Formulations capable of reacting with or removal of molecular oxygen

ABSTRACT

A composition includes a polymer, a functional component, and an oxidation catalyst. The functional component may be an oxidizable additive or a precursor thereof. The oxidizable additive includes an organic moiety including a first carbon atom (C1) attached to a hydrogen (H), a first group having a conjugated unit (a double bond, a triple bond, an aromatic ring); a second group having a heteroatom (including C═N, N═O, C═O, an O, a N, a fragment having at least three heteroatoms (including a N) within a spatial distance of 4 Å from C1); and a third group (hydrogen, an alkyl group, an aromatic group, a double bond, a triple bond, and a heteroatom). The C1 may be attached to a strong mesomeric electron-donating group and a strong mesomeric electron-withdrawing group; or to a conjugated group and a mesomeric group. The functional component may be derived from a recycled plastic article.

CROSS REFERENCE TO RELATED APPLICATIONS

This present application claims priority to and the benefit of U.S.Provisional Application No. 62/797,269 filed Jan. 26, 2019, which ishereby incorporated by reference in its entirety as if fully set forthbelow and for all applicable purposes.

TECHNICAL FIELD

Embodiments of this present invention relate to formulations capable ofreacting with or removal of molecular oxygen at ambient conditions. Morespecifically, embodiments of this present invention relate toformulations including oxidizable additives and optionally oxidizationcatalysts that react with molecular oxygen at ambient conditions forpackaging and other related applications.

BACKGROUND

Plastics are light, durable and recyclable, thus providing enormousutility in daily life. Particularly, plastics are common packagingmaterials for various applications. Contents found inside containersutilizing plastics vary from food, beverage and drugs, to cleaningproducts, gasoline, motor oil and many others. However, for variousoxygen sensitive materials, plain commercial plastics are often found tobe insufficient to protect the contents of the container from oxidativedegradation. This may be due to oxygen molecules that ingress from thesurrounding environment into the packaging interacting with the contentand causing oxidative degradations (or often called “spoilage”).Examples of the oxygen sensitive materials include certain food,beverage, pharmaceuticals, medical products, for human or for animals,electronic devices, corrodible metals or products and the like. Theincapability of plain commercial plastics from sufficiently fendingagainst the oxygen ingress may be due to the micro- or nano-sized poresthat are present throughout their structures through which oxygenmolecules may migrate in. While specialty plastics may be available toimprove such barrier properties, their costs are often prohibitive. Toovercome this problem, oxygen barrier additives are often utilized toimpede such oxygen ingress. The types and amounts of the barrieradditive required are determined by the contents of the packaging, theirsensitivity towards oxygen, as well as the required shelf lives of theproducts.

There are primarily two types of oxygen barrier additives, namelypassive barrier and active barrier. Passive barriers function byproviding a physical barrier towards gas molecules like oxygen. Thepassive barriers may be used as a coating on the surfaces of theplastics once they are in their finished shape. Typical examples includecarbon coating and silicon dioxide coating. In both cases, the coatingmaterial form a thin layer of dense material on top of the plastics toshield the plastics from being exposed to gas molecules. Alternatively,polymeric additives or nanocomposite additives may be doped as anadditive into the plastics structures themselves, such that theadditives forms road bumps, often in quasi-two-dimensional formats,towards the permeating gas molecules, thereby inhibiting theiringresses. The disadvantage of this approach includes, for example, thatpassive barriers cannot remove oxygen molecules that are introducedalong with the content during or before the filling (or packaging)process. Moreover, coating-type passive barriers typically require veryexpensive capital investment in specialized instruments in order toconduct such coating processes. As a result, the adoption of suchprocesses has so far not been widely accepted at the commercial level.

The second type of important barrier is so-called active barrierformulation. These formulations typically include an oxidizablemolecule, whether discrete, oligomeric or even polymeric, whetherinorganic or organic, that is oxidizable by molecular oxygen. Thisoxidizable molecule, once processed into a component of the container'splastic wall, reacts with the ingressed oxygen molecule before itpermeates into the cavity of the container. This removes the oxygenbefore it reaches the content of the container thus largely prohibitsthe oxidative degradations of concern. However, because majority of theapplication of such packaging containers operate at room temperature,the formulation will only be functional if the reaction between oxygenand the oxidizable molecules can proceed efficiently at roomtemperature. Almost invariably so far, this requires the presence of anoxidation catalyst, such as a cobalt carboxylate, in the formulation tofacilitate the oxidation reaction.

While existing machinery may be used to produce plastic packaging withactive barriers, other challenges are present. First, the currentlyavailable formulations are comparably expensive and can only be used forhigher-priced items. This has substantially limited the application ofactive barriers. In fact, there have been only a handful of productsthat entered the market in the past 30 years or so. This includes tradenames of Amosorb®, Oxbar®, MonOxbar®, DiamondClear®, OxyClear®,HyGuard®, Ageless®, and others relying on the same basic composition.Breakthroughs in this space are rare. Even these brands are always undercost, anesthetic, and/or regulatory pressures. Without effective barriermaterials, the brand owners have no choice but to resort to shorter-termsolutions which inevitably lead to not only food/beverage waste, butalso increasing plastics pollution. The market demand for new candidatesof oxygen scavenging technology is high.

Perhaps more concerning is that discrete low molecular weight additivesoften found in active barrier formulations may migrate out from thepolymeric matrices of the plastics walls and into the contents of thepackaging. Thus, if the contents are purity-sensitive for health,hygiene, or other reasons, the amount of such additives that may beintroduced into the packaging base resins often are very limited.Because a smaller initial concentration typically leads to a kineticallyslower chemical reaction, the performance of the formulation againstoxygen ingress is often also limited, at least at the beginning stage.While this concern may be partially mitigated by developing largermolecules or tethered molecules to reduce the mobility of the additives,other complications may occur. For example, large molecules such aspolymeric molecules often cause inhomogeneity with the matrix plastics,such that colors, hazes or other undesirable visual characteristics areproduced. Therefore, where transparency and colorlessness are important,such as in the case of food and beverage packaging, these active barrierformulations are not ideal without addressing the visual factor.Similarly, if the content is sensitive towards a light radiation of acertain color, the packaging is often designed to shield such color witha corresponding colorant. If the inhomogeneity caused by the activebarrier leads to a distortion of color from that initially designed, itmay be very difficult to compensate that distortion and bring the colorback into brand owner's specifications.

Additionally, another source for migration hazard comes from thefunctioning of the active barrier formulation themselves. As described,these formulations function because the oxidizable component of theformulation reacts with oxygen. Such a reaction often leads to bondcleavages and produces degradants smaller than the original oxidizablecomponent. Therefore, even when a polymeric additive is sufficientlyimmobile to avoid its own migration into and contamination of thecontents inside the plastic containers, their oxidative degradationproducts, which increases and accumulates over the entire life ofcontainer, may eventually reach a threshold to cause legitimateconcerns.

Furthermore, the functionality of the existing available active barrierformulations is still quite limited in various aspects. For example, anoxygen barrier additive may work with only a selection of availablecommercial plastics resins and does not work with the others.Additionally, an oxygen barrier formulation may work by itself or withonly a selection of available commercial additives (e.g. dyes andpigments, UV-inhibitors, antimicrobial agents, anti-slip agent), butdoes not work, or only work with much lower efficacy when otheradditives are present.

Also importantly for food, beverage, drug or similar applications, thecommercialization of a new formulation is a long process involvingvarious regulatory stages. Toxicological studies will often eliminateotherwise competent candidates for commercialization. Accordingly, it isdesirable to have a large selection of chemically functional candidatesbefore going into the latter stages of commercialization. The presentlyavailable knowledge in this area have not been sufficient to meet such aneed.

Therefore, there exists a clear need for a large selection of new, moreeffective, cheaper active barrier additives, or active barrier additivesthat are more compatible with base resins or additional additives, orthat improves upon various other aspects of these present shortcomings.For example, this will help reduce food spoilage—one key cause for theglobal problem of food waste at 1.3 billion tons of edible food peryear, and help maintaining food security and safety, among otherbenefits. Furthermore, improvements to other aspects of packagingapplication not described herein may also be desired. The objectives forembodiments of the present disclosure are to address one or morechallenges (e.g. scavenging effectiveness, safety, clarity,color-indication, cost) discussed above and below.

DETAILED DESCRIPTIONS OF THE INVENTION

As discussed above, there have been a need for new and improved activebarrier formulations. This is partly because of the deficiency of theseveral existing technologies noted above in this area of art. Thisinvention provides various different embodiments, aspects, sub-aspects,examples and instances, each to address one or more of thosedeficiencies, but does not attempt to solve all of them. Particularly,this disclosure targets to provide chemically functional embodiments,but does not take into account toxicology effects of those describedmolecules.

It is noteworthy that many of the prior alleged solutions, such asvarious patents and patent applications, often describe (and claim) amuch larger scope than that tested to be chemically functional for thedescribed purpose. For those portions of the disclosures, the issue ofenablement should be questioned and carefully evaluated. For example,there have been several functional oxidizable additives based onspecific chemical structures that include a benzylic or allylic C—Hfunctional group. Many of the patents and patent applications thereforeleap from these specific structures to broadly allege that all moleculeswith benzylic or allylic C—H groups are active molecules. Thesedisclosures, whether or not enabling for those specific chemicalstructures claimed, are not enabling prior art with respect to all othermolecules containing such functional groups. Indeed, it is wellrecognized in this industry that many molecules having merely benzylicC—H or allylic C—H do not function for the purpose of active barrieradditive. Notably, the specifications of these patents or patentapplications invariably fail to provide sufficient embodiments tosupport those broad assertions.

Such a problem, arguably prevalent in this area of art, may haveoriginated from a lack of appreciation of details of the specificreaction of concern, that is, oxidization reaction of an oxidizablemolecule by dilute molecular oxygen at an ambient temperature in a solidpolymeric matrix. In contrast, numerous scientific literatures describesimilar oxidization reactions that differ in one or more importantaspects. For example, vast majority of the scientific literature discussreactions utilizing pure oxygen as a reactant, at elevated temperatures,in presence of specialized catalysts outside the scope of thosedisclosures, or performed in liquid phases. It is well understood thatreactivities critically depend on actual conditions. Therefore, thosenumerous literature may have been relied upon to make theafore-mentioned improper generalizations cannot sufficiently support thedescribed scope of those patents and patent applications.

Similarly unsupported assertions with regards to other functional groupsas active oxidizable additives can also be found in the patents andpatent applications, which include, for example, unsaturatedpolyolefins, amines, polyamines, amides, polyamides, ethers, moleculeswith tertiary C—H bonds, polyalkyleneglycols, and any other moleculeswith a homolytic C—H bond dissociation energy of less than or equal toabout 93 kcal/mol. While the presence of these functional groups may notnecessarily preclude a molecule as an oxidizable additive, their merepresence does not indicate their activities. Other functional groups, orthe co-presence of other functional groups, are often necessary. Thosebroad assertations in the earlier literature can be disapproved by asimple experiment. Additionally, some of these prior alleged solutionsincludes or produces byproducts that makes them inappropriate for theintended applications. For example, some produce small molecules, suchas aldehydes, which makes them inappropriate for certain applications,such as food and/or beverage applications. For example, some cause hazeswhich makes them anesthetically unpleasing for marketing purposes. Forexample, some cause processing difficulty, such as screw slippery ininjection and/or extrusion operations. Therefore, while existingtechnologies may satisfy certain present demands, they are not perfectin every aspect and require further improvements.

The current invention provides many embodiments based on benzylic orallylic C—H, as well as many additional embodiments that do not rely onbenzylic or allylic C—H to function as an active barrier formulation. Insome embodiments, a single functional group provides the functionality.In some other embodiments, more than one functional group worksynergistically to provide the functionality. For example, a mesomericgroup and a conjugated group work synergistically, anelectron-withdrawing group and an electron-donating group, two mesomericgroups, and/or two conjugated groups work synergistically to provide thefunctionality. The present disclosure provides many embodiments,aspects, sub-aspects, examples, instances, and so on. Theseterminologies are used merely for the ease of organization anddescription. They shall all be interpreted as non-exclusive exampleswith varying breadths of coverage. They shall not be construed to beexhaustive. Additional embodiments, aspects, sub-aspects, examples,instances, and so on shall be construed to be within the scope of thedisclosure if a personal having ordinary skill in the art can reasonablyinfer those from the provided disclosure, embodiments, aspects,sub-aspects, examples, instances, and so on.

In describing the embodiments, aspects, sub-aspects, examples, andinstances, it is to be understood that all spatial (or stereo-) isomers,tautomers (isomers merely involving shifting of hydrogen atoms), andstructural isomers that do not involve change of the identities orbonding sequences of functional groups, are within the scope ofdisclosure if one of these isomers is disclosed in the specification,unless specifically noted otherwise. Therefore, unless clearlyspecified, a disclosure of a molecule with atomic groups in acis-configuration around a double bond also discloses the molecule withatomic groups in a trans- configuration around the double bond;disclosure of a molecule with one stereoisomer discloses all otherstereoisomers as well. In contrast, a disclosure of a molecule includinga toluene backbone with an additional substituent on the meta-positionrelative to the toluene methyl does not automatically disclose toluenewith a substituent on the para- or ortho-positions relative to thetoluene methyl, unless specified otherwise. This is because toluene withthe substitution on different positions does involve change of thebonding sequence of functional groups. However, a disclosure of such asubstituted toluene without specifying meta-, para-, orortho-configurations shall be construed to cover all these patterns.Also, disclosed functional groups may be substituted or unsubstitutedunless otherwise specified.

It is to be understood that all embodiments, aspects, sub-aspects,examples and instances provided here, unless specified otherwise, aredevoid of, and do not produce, a sufficient amount of free labilefragment(s) that inhibits the concerned reactivity of the oxidizableadditive and/or the reactivity associated with a necessary catalyst, orsuch an inhibition is remediated. The term “free labile” means that thefragment may be cleaved off during the processing and/or application ofthe composition of the embodiment and may be free to migrate to combinewith the catalyst (hence called “catalyst-deactivating unit”) and/orother portions of the oxidizable additive, thereby causing theinhibition. One example of remediation method for such inhibition effectis to use inert metal ions or compounds to scavenge and combine withsuch labile fragments so that they are not free to interact with activespecies (such as the oxidizable additive or the active oxidationcatalyst).

Furthermore, it is to be understood that a disclosure of a monovalent—R-H group also discloses a divalent —R— group, such as a compound witha ring including —R—, vice versa, unless a chemical formula (generic orspecific) indicates that the presence or absence of the —H. In certainsituations, cyclic compounds may be preferable for various reasons. Forexample, cyclic compounds are more resistant to be cleaved into smallerfragments, or the extra ring mandates certain configuration of thecompound which is beneficial. In other situations, cyclic compounds maybe less preferable. For example, the extra ring causes strain whichleads to unfavorable energetics; or the extra ring causesinaccessibility to the active site; or the extra ring mandates certainconfiguration of the compound which is undesirable. Additionally, adisclosure providing one molecule also discloses all polymeric moleculesthat derives from the molecule as a monomer or a co-monomer. Theconcentration of the molecule or co-monomer fragment in the polymericmolecules are of criticality. If the concentration is too high, therheology of the polymer composition may be substantially change to causeprocessing difficulty, and additional risks associated with themigration of the additive and/or degradants may increase. If theconcentration is too low, the effectiveness may be minimal. The properconcentration may be determined by routine experimentation, as describedlater. Likewise, if the disclosure provides a molecule, any derivatives,encapsulates, dendrimers, host-guess complexes, supramolecularcomplexes, of the molecule, either as a moiety covalently bound,ionically bound, datively bound, or not bound, are also within the scopeof the disclosure, provided that the presence of the encapsulatingspecies, additional functional groups, host, or guest species are notinhibiting to the oxygen scavenging reaction. For example, anencapsulating species that could chelate with a necessary metal catalyst(e.g. Co (II)) should not be used. The term “polymer” includes oligomersunless otherwise stated. So, for example, polyethylene glycol includesoligoethylene glycol.

The disclosure below recites various terms. The term “organometallic”shall be construed to encompass metalloids like boron, silicon, and tinin addition to other metals. Unless otherwise stated, the term “organic”includes “organometallic” provided that the metal is spaced away fromthe atom to which the organic component is attached by at least twobonds. The term “part,” “moiety,” “fragment,” “unit,” and “residue”shall be construed to be interchangeable with each other and to mean apart of a molecule or a molecular system. The disclosure of anycomponent, ingredient, member, constituents, or the like, of acomposition discloses that component, ingredient, member, constituent inpure form (unless otherwise stated). Therefore, for example, disclosureof a polymer do not encompass the polymer with residue catalystremaining in the polymer matrix. The disclosure below also recites“proximity” to describe spatial relationship between different parts ofa molecule or molecular system (hereinafter collectively “molecule”).This term shall be interpreted to include both the embodiment in whichthe different parts are directly bonded together, and the embodiment inwhich the different parts electronically communicate with each other andare spatially close to each other within a certain threshold but notdirectly bonded. For example, the disclosure may provide a moleculeinvolving a carbon center (C1) in proximity with a moiety R1. This shallbe interpreted to mean that, in the natural ground state of themolecule, the atom of interest within the first moiety R1, denoted asA1, is within a certain threshold of direct point-to-point distance fromC1. The atom of interest A1 is the atom that embodies most of theconcerned effect of R1 towards C1. For example, if an electron-donatingeffect to C1 is of concern, A1 is selected to be the atom that has thestrongest electron-donating effect on C1, such as the closest atom to C1that has a free lone pair. For another example, if electron-withdrawingeffect to C1 is of concern, A1 is selected to be the atom having thestrongest electron-withdrawing effect on C1. The threshold is determinedbased on the identity of the A1 atom and is evaluated based onequivalents to certain numbers of typical A1—C single bond length inorganic or organometallic molecules. A1 and C may be directly bonded ornot bonded. Alternatively, the term “proximity” may also be interpretedto mean that, in the natural ground state of the molecule, A1 is withina certain threshold of direct point-to-point distance from the hydrogenatom attached to C1 and closest to A1. The threshold is determined basedon the identity of the A1 atom and is evaluated based on equivalents tocertain numbers of typical A1—H bond length in organic or organometallicmolecules. These typical bond lengths may be those provided by commonchemistry textbooks, CCBDB database of experimental bond lengths fromNIST, or properly computed by the state of art computational chemistry.For example, a typical C—H bond is 1.09 Å; while a typical O—H bond is0.97 A. For another example, a hydrogen bond distance is useful. Astrong hydrogen bond has distances of 2.2-2.5 Å; a moderate hydrogenbond has distances of 2.5-3.2 Å; and a weak hydrogen bond has distancesof 3.2-4.0 Å. In one aspect, C1 and A1 are directly bonded with eachother; in another aspect, C1 and A1 are covalently bonded via aplurality of bonds; alternatively, there may be no direct bond betweenC1 and A1. In a one aspect, direct bonding is preferred due to thestronger interactions between C1 and R1; while in another aspect, theabsence of bonding is preferred due to various reasons, such as to leaveopen direct bonding sites for other necessary substituents, or toprovide the flexibility of arranging multiple moieties around the C1center without causing large strains, etc. The spatial distances may bemeasured by any known method, for example, crystallography andcomputational chemistry.

The disclosure below also describes various types of electroniccommunications. These communications may be through-bond orthrough-space. Having a covalent bond between two moieties is oneexample of electronic communication. Ionic and electrostatic effects,electronic, spin, radical delocalization and polarization, conjugation,hyperconjugation, steric effects, coordinative or dative interactionsare also electronic communications. Particularly, this disclosuredescribes the effects of electron-withdrawing or electron-donatingeffects. For example, this disclosure describes electron-withdrawinggroups (“EWG”), or electron-donating group (“EDG”) with respect to acertain carbon atom. These terminologies are used in reference to thecarbon atom and the hydrogen atoms attached to the carbon atom. The samegroup may have other or even opposite effect to a different atom itattaches to. For example, an ester carboxylate group(—C^(a)(═O^(a))—O^(b)—) attached to C1 with C^(a) and to C2 with O^(b)is typically an EWG to C1 but an EDG to C2.

Additionally, the designation of EWG or EDG may change based on chemicalenvironment of the substituent, especially for weak-effect substituents.For example, vinyl group is generally regarded as a weak EDG when it isfree of any substituent on itself; but it may be regarded as a weak EWGwhen it bears electron withdrawing groups such as halogens, nitro,cyano, and the like.

Furthermore, the EWG effect or EDG effect may either be of a mesomericnature or of an inductive nature. Unless specified, an EWG substituentshall be construed to encompass any substituents that has either amesomeric EWG effect or an inductive EWG effect, whether or not thatparticular effect is the dominating effect of the substituent. Forexample, cyano group (—CN) has both mesomeric electron-withdrawingproperty and inductive electron-withdrawing property. Therefore, cyanogroup is encompassed by the designations of EWG, mesomeric EWG andinductive EWG. For another example, cyanomethyl (—CH2CN) only hasinductive electron-withdrawing property. So it is encompassed by thedesignations of EWG and inductive EWG. For a further example, amino(—NH₂) has both inductive electron-withdrawing property and mesomericelectron-donating property. It is encompassed by the designations ofEWG, EDG, inductive EWG and mesomeric EDG. For yet a further example,isocyanate and isothiocyanate each has both inductiveelectron-withdrawing property and mesomeric electron-donating property.In other words, one substituent may possess simultaneously two or moresubstituent effects. Generally, aromatic groups (includingheteroaromatic groups), other conjugated groups, as well as heteroatoms(e.g. O, N, S, etc.) have some mesomeric EDG or EWG effects; and some ofthem may simulataneously have some inductive EDG or EWG effects.

Different EWGs and EDGs have different strengths. A “moderate mesomericEWG” refers to an EWG that has a mesomeric electron-withdrawing effectthat is similar to that of an aldehyde (—CHO) group, a ketone (—COR)group, a carboxylic acid (—COOH) group, an acyl chloride (—COCl) group,an esters (—COOR) group, and an amide (—CONH₂) group. A “strongmesomeric EWG” refers to an EWG that has a mesomericelectron-withdrawing effect that is stronger than those of a moderatemesomeric EWG. For example, a strong mesomeric EWG may be a cyano (CN)group, a triflyl (—SO₂CF₃) group, a sulfonate (—SO₃H) group, a nitro(—NO₂) group, etc.. A “weak mesomeric EWG” refers to an EWG that has amesomeric electron-withdrawing effect that is weaker than those of themoderate mesomeric EWG. A “moderate mesomeric EDG” refers to an EDG thathas a mesomeric electron-donating effect that is similar to that of anamide (—NHCOR) group and an ester (—OCOR) group. A “strong mesomericEDG” refers to an EDG that has a mesomeric electron-donating effect thatis stronger than those of a moderate mesomeric EDG. For example, astrong mesomeric EDG may be a phenoxide (—O⁻) group, an amine (—NR₂,—NHR, —NH₂) group, an ether (—OR) group, and a hydroxy (—OH) group, etc.A weak mesomeric EDG may be any EDGs that are weaker than the moderatemesomeric EDG. A “moderate inductive EDG” refers to an EDG that has aninductive electron-donating group effect that is similar to that of acarboxylate anion (—COO⁻). A “strong inductive EDG” refers to an EDGthat has an inductive electron-donating effect that is stronger thanthose of a moderate inductive EDG. For example, a strong inductive EDGmay be trihydroxy boron (—B(OH)₃), a divalent butyl group (—(CH₂)₄—), adivalent propyl group (—(CH₂)₃—). A “weak inductive EDG” refers to an

EDG that has an inductive electron-donating effect that is weaker thanthose of a moderate inductive EDG. A “moderate inductive EWG” refers toan EWG that has an inductive electron-withdrawing group effect that issimilar to that of a carboxylic acid (—COOH) group, a hydroxy (—OH)group, an ether (—OR) group, an amine (—NR₂, —NHR, —NH₂) group. A“strong inductive EWG” refers to an EWG that has an inductiveelectron-withdrawing effect that is stronger than those of a moderateinductive EWG. For example, a strong inductive EWG may be cyano (CN)group, a nitro (—NO₂) group, a nitrosyl (—NO) group, an ammonium (—NH₃⁺, —NR₃ ⁺) group, etc.. A “weak inductive EDG” refers to an EDG that hasan inductive electron-donating effect that is weaker than those of amoderate inductive EDG.

Additionally, the disclosure describes “conjugated groups” or“conjugated units.” These terms shall be construed broadly to encompasstraditional aromatic groups, simple double bonds, simple triple bonds orthe combinations thereof. Note that the term “double bond” and “triplebond” refers to a chemical group having not only the bond, but also theatoms the bond immediately connects, unless otherwise stated. Therefore,for example, the phrase “a first atom A₁ connected to a double bond”refers to A₁−X═Y rather than A₁═X, where X and Y are any atoms.Embodiments of conjugated groups may include only carbon or may includeheteroatoms. Heteroatom includes, for example, O, N, P, S, Si. The terms“conjugated group” and “conjugated unit” may further includehyperconjugation when the electron delocalization effect is of amagnitude not negligible, for example, when a lone pair is involved.Therefore, for example, benzoic acid includes a conjugated group thatextends not only to the benzene ring, the C═O, but also the hydroxyoxygen atom. However, a σ-bonded carbon atom to a double bond or benzenering does not have delocalization effect of such a magnitude, and shouldnot be considered a “conjugated group.” Also, it is to be understoodthat conjugation is inherently a mesomeric effect. Therefore, allconjugated groups may also be designated as either EWG/mesomeric EWG orEDG/mesomeric EDG. Additionally, when the conjugated group includeheteroatoms, inductive effect may be present. For example, 2-pyridyl isan inductive electron-withdrawing group due to the close proximity of anelectronegative atom (N). At the same time, it is also a mesomericelectron-donating group. In other words, 2-pyridyl is encompassed bydesignations of conjugated group, EDG, EWG, inductive EWG and mesomericEDG. It is further to be understood that in providing a certain chemicalstructure, a drawing or a formula presented in different ways may be fora same molecule. For example, —COR, —C(═O)R, and —C(═O)—R all illustratea carbonyl group attached to a residue R.

The disclosure also describes homolytic bond dissociation energies(BDE). Homolytic BDE (or abbreviated herein as BDE) is one measure ofthe strength of a chemical bond, such as that of A-B. It is defined asthe standard enthalpy change when A-B is cleaved by homolysis to giveradical fragments A. and B.. This parameter is temperature dependent.Unless otherwise specified, the BDE described in this disclosure areBDEs at 298 K. Any suitable experimental techniques available to aperson of ordinary skill in the art may be used to determine BDE. Thesetechniques include, for example, spectrometric determination of energylevels, generation of radicals by pyrolysis or photolysis, measurementsof chemical kinetics and equilibrium, various calorimetric andelectrochemical methods, and derivations from known data based on thefirst law of thermodynamics, as well as quantum chemistry computations.It is to be understood that bond dissociation energy measurements arechallenging and are subject to considerable error. According toComprehensive handbook of chemical bond energies, Luo Y R (2007), BocaRaton: CRC Press, ISBN 978-0-8493-7366-4, OCLC 76961295 (“Luo”), themajority of currently known values are accurate to within ±1 or 2kcal/mol, while values measured in the past, especially before the1970s, can be especially unreliable and have been subject to revisionson the order of 10 kcal/mol. The BDE numbers provided here for specificmolecules or fragments shall be construed as BDEs measured by the mostaccurate method available to the inventor, to the best ability of theinventor, although subject to experimental errors. The experimentalerrors may include systematic errors for, e.g. the method used anddisclosed, as well as accidental error for specific molecules.Additionally, thermal fluctuation provides minor but additionaluncertainty. The magnitude of this uncertainty is dependent on thetemperature of the application. At room temperature, it is about 0.59kcal/mol. The various BDE numbers provided here as thresholds should beconstrued to be true BDEs, subject only to the systematic error andthermal fluctuations at the application temperature. A person of skillin the art shall use the most accurate method available to date todetermine the BDE in using this disclosure.

The disclosure further discloses energy gaps and strains. Each moleculehas an internal energy that consists of all the energy stored within themolecule. The difference in internal energies of related species, suchas a molecule R-H and its radical R., may be evaluated as energy gaps.The significance of the energy gap will become apparent to a personhaving ordinary skill in the art reading the subsequent sections. Wheneach atom of a molecule is in their preferred geometry, the molecule hasits lowest internal energy and is considered to be in its natural groundstate. When the molecule interacts with its environment or when itundergoes certain transformations, such as bond formation, bondcleavage, formation of transition state, etc., the atoms involved oftenare forced into a less preferred geometry. This causes the internalenergy of the molecule to be raised. The amount of extra internalenergy, or “strain” energy, is somewhat like the energy stored in acompressed spring. The strain may be categorized into steric strains orVan de Waals strains, torsional strains, and ring strains. Often times,more than one type of strain occur simultaneously. Further notably,while strain increases internal energy of the molecule, in certainsituations, additional energy factors, such as delocalization, may causethe internal energy of the molecule to drop simultaneously. Therefore,the overall internal energy of the molecule may not necessarilyincrease. Strains, energy gaps, and other energy factors may be measuredin the units of energy, such as kcal/mol, by any suitable experimentaltechniques available to a person of ordinary skill in the art. Thesetechniques include, for example, spectrometric determination of energylevels, generation of radicals by pyrolysis or photolysis, measurementsof chemical kinetics and equilibrium, and various calorimetric andelectrochemical methods, as well as quantum chemistry computations.

It is to be understood that different applications may require differentlevels of oxygen scavenging activity. Therefore, it may be desirable tohave a numeric measure for the predicted activity to facilitatecomparisons and selections. Oxidation Reactivity Index (OI) and OverallOxidation Reactivity Index (OOI) are two measures of oxygen scavengingcapability. Of these two indices, OI takes into account the propertiesof different fragments of the molecule as related to oxygen reactivity,such as the electron-donating effect, electron-withdrawing effect,steric effect, conjugation effect, certain interaction with catalysts;and OOI evaluates the molecule as a whole as relevant to oxygenscavenging capabilities. Both these indexes for various specificmolecules and functional groups are under current development. They willbe released, as they become available, at the website known by the URL“https:sites.google.com/site/o2scavenger/”. If this website addressbecomes unavailable due to, such as, changes of provider's offerings, analternative website address will be provided at the inventor's LinkedInprofile.

It is also to be understood that the selection of active barriers oftendepends on the specific application contexts. For example, for packagingapplications using primarily polyethylene terephthalate (PET) resins andwhen clarity is important, an additive that includes primarily saturatedC—C bonds may not be appropriate for aesthetic reasons as they tend toinduce hazes or colors. For another example, certain chemicallyfunctional active barrier formulations may not be appropriate for food,beverage or drug packaging, if one or more of its components, or thedegradation products thereof, contain unacceptable toxicology effects.The term “pharmaceutically acceptable” refers to those compositionswhich are, within the scope of sound medical judgment, suitable for usein contact with the tissues of humans and lower animals without unduetoxicity, irritation, allergic response and the like, and arecommensurate with a reasonable benefit/risk ratio. Pharmaceuticallyacceptable compositions are well known in the art. For example,pharmaceutically acceptable salts are described in detail in S. M. Bergeet al., J. Pharmaceutical Sciences, 1977, 66, 1-19 (“Berge”),incorporated herein by reference. Similarly, “food and/or beveragecontact acceptable” refers to those compositions which are, within thescope of sound medical judgment, suitable for use in contact with foodand/or beverages without causing undue toxicity, irritation, allergicresponse and the like related to the ingestion of the food and/orbeverage, and are commensurate with a reasonable benefit/risk ratio.

It is also to be understood that while the embodiments described belowfocus on active oxygen barrier formulations, such active oxygen barrierformulation may include additional functionalities, such as being apassive barrier at the same time (such that it functions to not onlyimpede oxygen ingress, but also impede, in for example beerapplications, carbon dioxide loss from inside the container). Also, thevarious embodiments provided may be implemented as a single-layerpackaging material, or may be implemented as one of the inner layers ofa multi-layer packaging material, or one of the outer layers of amulti-layer packaging material. The packaging application may be rigidcontainers, or may be flexible packaging.

Additionally, these formulations may be used in relevant but differentcontexts. For example, sachets or inserts, cap liner, sealants or thelike that contain the disclosed formulations may be introduced into thecavity of the container separate from the container molding or formingprocesses. They may also be provided as part of a closure to thecontainer. In addition to impede oxygen ingress, these sachets orinserts may also be used to scavenge oxygen contained inside thepackaging immediately following filling of the contents (as opposed toimpede oxygen ingress over time from the outside of packaging). Foranother example, plastics with the disclosed formulations may be used ascoatings inside or outside other types of containers to provide betterfunctionality with respect to oxygen scavenging, color indication orother relevant characteristics. Even furthermore, while this disclosureis provided in the context of packaging applications, it is to beunderstood that the concepts apply to all other types of reactionsprovided that the reactive environment of the other applications aresimilar in relevant aspects, for example, reactions at ambienttemperature in solid states within atmospheric environment.

These varying contexts of application determines the amount of theoxidizable additive to be used. The oxygen sensitivity of the protectedcontent is another crucial consideration. In applications for food andbeverage plastics additives, for example, the amount is typicallybetween 0.1% to 30%. If the amount is too small, such as less than 0.1%,the effectiveness will be minimal; if the amount is too large, increasedrisk associated with the migration or degrade of the additivesthemselves may become more problematic. For applications as an oxygenabsorber, the amount may be between 0.01% to 100%.

The disclosure below also describes catalysts. Unless otherwisespecified, the catalysts are present in the composition at acatalytically effective amount, that is, at an amount sufficient tosubstantially affect the rate of chemical reaction in question (forexample, an oxidation, hydrolysis, transesterification, ortransesteramidation reaction, etc.) The disclosure also describesprecursors to oxidative additives. This term refers to one or morereactants from which the oxidative additives form, under the regularprocessing condition of the composition. Therefore, where A and B reactunder a certain condition to form oxidizable additive C, A, B, andcombination thereof are each a precursor to C if, and only if, thecertain condition is one typical to the processing of A, B, and/or C.Otherwise, none is a precursor to C.

In addition to providing active barrier solutions, this disclosure alsoprovides various other additional methods, matters, and compositionsinside or outside packaging art. In one aspect, the disclosure providesnovel synthetic procedures for several relevant additive moleculesherein described. These synthetic procedures have additional utilitiesbeyond what has been so-far described and shall be so construed andapplied. For example, the disclosure provides that production of certainactive barrier additives may start from a recycled plastics material asa starting material as opposed to traditionally sourced raw chemical.Such a method for synthesis of that additive alone, without regard toapplications, constitutes a method of plastics recycling havingsustainability and environmental remediations impacts. Such a method maybe applied by a person having ordinary skill in those different arts andoutside the area of active barrier packaging. Similarly, this disclosureprovides examples in which the oxidizable additive changes color as itreacts with oxygen and degrades as a result. This provides acolor-indicator for the shelf-life for the packaging with respect tooxygen barrier effectiveness. Furthermore, this disclosure providesexamples of a method of improving transparency of polyesters whencondensation polymers are used as a component of the barrierformulation. Still furthermore, certain ammonium cation-based oxygenscavenger disclosed herein may be applied to simultaneously addressanti-microbial needs; and some triazine-based oxygen scavenger may beapplied to address UV-blocking needs. In some examples, thesesimultaneous applications interact with each other to alter the effectof oxygen scavenging. Even further, this disclosure provides a method ofreactive extrusion which may be used in a variety of other applicationsinvolving condensation polymers. These practical aspects of theinvention shall not be limited to the applications of barrier packaging,but may be extended to any similar or related applications that involvessimilar or related issues.

With respect to color-indicator for the shelf-life with respect tooxygen barrier effectiveness, various examples below providerepresentative molecules whose structures change as response tointeraction with oxygen molecules. Without being limited by theory,these structural changes usually involve extension or break-down of theconjugation systems of the molecules thereby changing the way themolecule interacts with light. One consequence is that the productmolecule following the reaction with oxygen will typically absorb alight radiation that is of a different wavelength than the unreactedmolecule does. Another consequence is that the product molecule mayprovide an emission that the unreacted molecule does not provide, or anemission at a wavelength different from that provided by the unreactedmolecule. If such absorption or emission is within the visible lightregion, for example, between 400 nm and 700 nm, the color change of theoxidizable additive will be noticeable by human eyes. Because the colorchanges are the direct result of the consumption of the oxidizableadditive via its reaction with oxygen, such color change is directlyrelated to the then-available concentration of the additive present inthe system, which in turn may be related to the expected shelf life.Even when the light radiation of the absorption or emission is outsidethe visible light region, spectrometers or other instruments may be usedto detect such change in concentrations of the additive thereby provideindication for remaining shelf-life. Because emission is typically morecharacteristic and less prone to interference, utilization of emission(such as fluorescence and phosphorescence) is preferred.

Generally, the active barrier formulation includes an oxidizableadditive and an oxidation catalyst. The catalyst may be optional whenthe oxidizable additive has a sufficiently high activity, as describedbelow.

Oxdizable Additive

Surprisingly, one or more of the challenges presented earlier may beaddressed by utilizing an oxidizable additive or a precursor thereof asfollows. In a first embodiment of the present invention, the formulationincludes a discrete, oligomeric, or polymeric component that is selectedfrom an oxidizable additive and a precursor to the oxidizable additive,wherein said precursor is capable of being converted into the oxidizableadditive during processing or application of the formulation. Theoxidizable additive comprises an organic or organometallic componentincluding a first carbon atom, denoted as C1, attached to a hydrogenatom and surrounded by three moieties R1, R2, and R3. In someembodiments, two or more of the moieties R1, R2, and R3 functionsynergistically to lead to oxygen scavenging activity at the C1—H site.Particularly, C1—H bond becomes weaker than without one, two, or threeof those moieties. This is not to say a molecule with only one of suchgroups would necessary fail to function. However, in many examples,higher activities are reached due to the synergistic effect. For a firstexample, the first carbon atom C1 is directly bonded to at least one ofR1, R2, and R3. For a second example, the first carbon atom C1 isdirectly bonded to R1, R2, and R3. In a third example, at least one ofR1, R2, and R3 is covalently directly bonded to at least another one ofR1, R2, and R3. In a fourth example, at least one of R1 and R3 arebonded covalently to C1, and the at least one is also directly bonded toR2. In a fifth example, R1, R2, and R3 are not bonded to one another.

In a first aspect of the first embodiment, R1 includes a conjugatedgroup directly attached to C1 with an atom selected from (1) an atom ofsp² hybridization pattern, and (2) an atom of sp hybridization pattern;R2 includes a mesomeric group selected from a mesomeric electrondonating group, a mesomeric electron-withdrawing group, and anotherconjugated group; and R3 is selected from a hydrogen (H), an organicresidue and an organometallic residue.

The following description details options for R1 and options for R2independent of each other's selection. Each such R1 option may becombined with each such R2 option unless stated otherwise or chemicallyimpossible, such as when valence cannot be satisfied, or when thecombination leads to unstable compound. In a first sub-aspect of thefirst aspect of the first embodiment with respect to the substituent R1,R1 includes a benzene ring directly attached to C1. For example, R1 isselected from a phenyl, a naphthyl, a phenanthrenyl, an anthracenyl, aquinolinyl attached to C1 at one of the four atoms belonging to thebenzene portion of the fragment, and the like. In a second sub-aspectwith respect to the substituent R1, R1 does not include a benzene ringdirectly attached to C1. The non-benzene conjugated group may be, forexample, an alkenyl, an alkynyl, and the like. These substituents havesmaller volumes, therefore asserts a smaller steric effect.Alternatively, the non-benzene conjugated group may be, for example, apyridyl, a pyrrolyl, a thiophenyl, a furanyl, a quinolinyl attached toC1 at one of the four atoms belonging to the heteroatom ring portion ofthe fragment, and the like. These substituents have larger volumes,therefore asserts a greater steric effect. In a third sub-aspect withrespect to the substituent R1, R1 may include a —X═Y double bond,wherein X is directly connected to C1 and selected from N, P, CR^(a),N(═O), and P(═O), and Y is independently selected from an O, S, NR^(a),N(═O)R^(a), PR^(a), P(═O)R^(a), and CR^(b)R^(c), wherein R^(a), R^(b),R^(c) is each independently selected from H, an organic residue and anorganometallic residue. For example, R1 includes a C═C double bond (suchas a vinyl group and derivatives thereof) directly connected to C1. Foranother example, R1 does not include a C═C double bond directlyconnected to C1, and R1 includes, for instance, where R1 includes animido (—N═CR^(b)R^(c)) group, wherein R^(b) and R^(c) is eachindependently selected from H, an organic residue and an organometallicresidue. For another instance, R1 includes an imido (NR^(a)═CR^(b)—)group, wherein R^(a) and R^(b) is each independently selected from H, anorganic residue and an organometallic residue. In a fourth sub-aspectwith respect to the substituent R1, R1 is a conjugated group havingelectron-donating effect. For example, R1 is a phenyl group not attachedto an electron-withdrawing group. In a fifth sub-aspect with respect tothe substituent R1, R1 is a conjugated group having electron-withdrawingeffect. For example, R1 is a cyano —CN group. In a sixth sub-aspect withrespect to the substituent R1, R1 includes an extended conjugated groupincluding two or more substituents described above and bonded togetherat an atom of either sp² or sp hybridized patterns. For example, R1 is abenzoyl group (Ph-C(═O^(a))—O^(b)—) attached to C1 with O^(b). In aseventh sub-aspect with respect to the substituent R1, R1 includes asubstituent with a substituent effect opposite that of the mesomericelectron donating group or a mesomeric electron-withdrawing group of R2.Additionally to sterics, the selection of proper groups may also takeinto account the flexibility of the fragment and the availability foraccess to the C1 site. These same considerations for selecting R1 arealso at play for R2, R3 in this embodiment and subsequent embodiments.

With respect to R2, several sub-aspects are available as well, eachindependent from the selection of R1. In a first sub-aspect with respectto R2, R2 is a second conjugated group. All available options for R1 arealso available for R2. For example, R2 includes a benzene ring directlyattached to C1. For another example, R2 does not include a benzene ringdirectly attached to C1. For a further example, R2 includes a C═C doublebond directly attached to C1. For yet another example, R2 does notinclude a C═C double bond directly attached to C1. For yet a furtherexample, R2 includes imido (—N═CR^(b)R^(c)) group, or imido(NR^(a)═CR^(b)—) group, wherein R^(a), R^(b) and R^(c) are eachindependently selected from H, an organic residue and an organometallicresidue. In a second sub-aspect of the first aspect with respect to R2,R2 includes a mesomeric electron donating group. For example, R2includes one of a thiolate anion (—S⁻) group, an oxide anion (—O⁻)group, an amine (—NR², —NHR, —NH₂) group, an ether (—OR) group, and ahydroxy (—OH) group, amide (—NHCOR) group, an ester (—OCOR) group, asulfonamide (—NHS(═O)₂R) group, a styryl (—CH═CH—C₆H₅) group, aferrocenyl group, a triphenylphosphine imide (—N═P(C₆H₅)₃) group, athiol (—SH) group, a phosphonic dichloride (—P(═O)Cl₂) group, anisocyanate (—N═C═O) group, an alkyl groups, a methylenedioxy (—OCH₂—)group, a vinyl (—CH═CH₂) group, a trialkyltin (—Sn(CH₃)₃) group, a furylgroup, a thienyl goup, a tetramethylsilane (—CH₂—Si(CH₃)₃) group, and soon. All these groups may be further substituted to enhance theelectron-donating ability.

In a third sub-aspect with respect to R2, R2 includes a mesomericelectron withdrawing group. For example, R2 includes a cyano (CN) group,a triflyl (—SO₂CF₃) group, a trihalide group (—CF₃, —CCl₃), a sulfonate(—SO₃H) group, a nitro (—NO₂) group, a nitrosyl (—NO) group, an aldehyde(—CHO) group, a ketone (—COR) group, a carboxylic acid (—COOH or —COO⁻)group, an acyl chloride (—COCl) group, an esters (—COOR) group, and anamide (—CONH₂) group, a nitrogen cation (—N⁺≡N) group, an arsenic acid(As(O)(OH)₂ or AsO₃H⁻) group, a sulfonamide (—S(═O)₂NHR, (—S(═O)₂NR₂)group, a trifluoromethyl (—CF₃) group, methylsulfinate (—SO₂(CH₃))group, methylsulfenate (—SOCH₃) group, thiocyanate (—SCN) group, alkyne(—C≡CH) group, vinyl with strong electron-withdrawing groups (e.g.—CH═CH—NO₂), a dialkyl phosphoryl (—P(═O)R₂) group, a dialkylthiophosphoryl (—P(═S)R₂) group, a dialkylphosphine (—PR₂) group, atetramethylphosphonium (—P(CH₃)₄ ⁺) group, pyridyl groups, a benzoxazolegroup, a benzothiazolyl group, a conjugated group or hyperpolarizableatom directly bonded to perfluorinated alkyl groups. All these groupsmay be further substituted to enhance the electron-withdrawing ability.For example, fluoromethylsulfinate (—SO₂(CF₃), —SO₂(CHF₂)) group,fluoromethylsulfenate (—SOCF₃, —SOCHF₂) group.

In a fourth sub-aspect with respect to R2, R2 directly bonds to C1. Forexample, R2 includes carbonyl wherein the carbonyl carbon directly bondsto C1 covalently. In a fifth sub-aspect, R2 is spatially proximal to theC1 although not covalently attached. For example, R2 includes apolybutylene glycol oligomer or polymer fragment, wherein one of theglycol oxygen atoms is spatially proximal to and in electroniccommunication with C1. In a sixth sub-aspect, R2 is spatially proximalto and in electronic communication with the hydrogen atom attached to C1although not covalently attached. For example, R2 includes a polyamineoligomer or polymer fragment, wherein one of the amine nitrogen atom isspatially proximal to the hydrogen atom attached to C1 and asserts anelectron-withdrawing effect.

In a seventh sub-aspect with respect to R2, R2 includes a mesomericsubstituent of a formula Q(CZ₁Z₂-Ar₁)(CZ₃Z₄-Ar₂), wherein the Ar₁ andAr2 are each independently selected from an aryl and a heteroaryl whichis each independently substituted with 0, 1, 2, or 3 groupsindependently selected from halogen, C1-C4 alkyl, and electronwithdrawing groups and valence is satisfied, Z₁-Z₄ each independentlyselected from hydrogen, halogen, C1-C4 alkyl, electronic withdrawinggroup, electronic donating group, or collectively ═O; provided that atleast one of the Z₁, Z₂ set and Z₃, Z₄ set are hydrogens; Q is selectedfrom N and P and directly bonds to C1, and R1 includes an aryl or aheteroaryl.

In an eighth sub-aspect with respect to R2, R2 includes a mesomericsubstituent is of a formula other than those described in the seventhsub-aspect. For example, R2 includes the same formula as described abovefor the seventh sub-aspect with the exception that Q is selected fromP═O and N═O with either the phosphorous P atom, or the nitrogen N atomattached directly to C1. For another example, R2 includes the sameformula as described above for the seventh sub-aspect with the exceptionthat at least one of Ar₁ and Ar₂ is replaced with a —X═Y double bond,wherein X directly connects to carbon atom which in turn directly bondedto Q and is selected from N, P, and CR^(a), and Y is independentlyselected from an O, S, NR^(a), PR^(a), and CR^(b)R^(c), wherein R^(a),R^(b), R^(c) is each independently selected from H, an organic residueand an organometallic residue. For yet another example, R2 includes thesame formula as described above for the seventh sub-aspect with theexception that both of A₁ and Ar₂ are each replaced with a —X═Y doublebond, wherein the —X═Y group is independently defined as follows: Xdirectly connects to carbon atom which in turn directly bonded to Q andis selected from N, P, and CR^(a), and Y is independently selected froman O, S, NR^(a), PR^(a), and CR^(b)R^(c), wherein R^(a), R^(b), R^(c) iseach independently selected from H, an organic residue and anorganometallic residue. For a further example, R2 includes the sameformula as described above, and R1 is other than an aryl or a heteroarylgroup.

For each of the above sub-aspects with respect to either R1 or R2, R1and R2 may be covalently bonded together to form a ring. Alternative, R1or R2 may be covalently bonded to R3 to form a ring. For example, bothR1 and R2 are phenyl groups directly attached to Cl, wherein R1 and R2are also covalently bonded at the position ortho- to C1 for bothphenyls. In other words, R1, R2, and C1 collectively form a flurorenefragment. For another example, R1 is a phenyl group, R2 is an amidegroup attached to C1 with the nitrogen atom, wherein the carbonyl of R2is directly bonded to R1 to form a five-member ring. In other words, R1,R2, and C1 collectively form a dihydrophthalimide fragment. In varioussituations, it may be preferable to include ring as it helps reduce theproduction of small migrants from oxidations, and help increase thereactivity to oxidation reaction. In some embodiments, C1, R1, and R2collectively determine the reactivity.

Representative examples of the present embodiment may be understood inreference to the following examples of specific R1, R2, and R3. For afirst example, R1 includes a phenyl attached directly to C1, R2 includesa phenyl attached directly to C1, and R3 is hydrogen (BDE=84.7). For asecond example, R1 includes a phenyl attached directly to C1, R2includes a C═C double bond directly attached to C1, and R3 is an ethylgroup. For a third example, R1 includes a phenyl attached directly toC1, R2 includes a C≡C triple bond attached directly to C1, and R3 is ahydrogen (BDE=80.0). For a fourth example, R1 includes a C═C double bondattached directly to C1, R2 includes a C≡C triple bond attached directlyto C1, and R3 is a carboxylic group (—COOH). In a fifth example, R1includes a C═C double bond directly attached to C1 on a first doublebond carbon atom C2, C2 attached to the carbonyl carbon atom of acarboxylic acid or ester group, R2 includes a carboxylic acid or estergroup with its carbonyl carbon attached to C1, and R3 is hydrogen(BDE=87.8). In a sixth example, R1 includes a benzene ring directlyattached to C1, R2 includes a carboxylic acid or ester group with thecarbonyl carbon attached to C1, and R3 is a hydrogen (BDE=84.9). In aseventh example, R1 includes a benzene ring directly attached to C1, R2includes a carboxylic acid or ester group with the carbonyl carbonattached to C1, and R3 includes a hydroxyl or alkoxy group (BDE=75.5).In an eighth example, R1 includes a benzene ring directly attached toCl, R2 includes a carboxylic acid or ester group with the carbonylcarbon attached to C1, and R3 includes an ester with the non-carbonyloxygen atom attached to C1 (BDE=79.1, 86.1). In a ninth example, R1includes a benzene ring directly attached to C1, R2 includes an amidegroup with the carbonyl carbon attached to C1, and R3 includes an alkylgroup such as n-butyl group. In a tenth example, R1 includes a benzenering directly attached to C1, R2 includes a carboxylic acid group or anamide group with the carbonyl carbon attached to C1, and R3 includes anamine group directly attached to C1 with the amine nitrogen atom(BDE<85.7). In an eleventh example, R1 includes a benzene ring directlyattached to C1, R2 includes a carboxylic acid group or an amide groupwith the carbonyl carbon attached to C1, and R3 includes a hydroxy oralkoxy group directly attached to C1 with the oxygen atom (BDE<85.7).

For a twelfth example, R1 includes a C═N double bond with its carbon endattached to C1, R2 includes a phenyl ring attached directly to C1, andR3 is hydrogen. For a thirteenth example, R1 includes a C═C double bonddirectly attached to C1, R2 includes a C═N double bond with its nitrogenend attached to C1, R3 is a methyl group (BDE=59.8). For a fourteenthexample, R1 includes a phenyl ring attached directly to C1, R2 includesa C═N double bond with its N end directly attached to C1, and R3 ishydrogen (BDE˜76.0). For a fifteenth example, R1 includes a phenyl ringattached directly to C1, R2 includes a C═N double bond with its N enddirectly attached to C1, and the carbon end of the C═N double bond isdirectly bonded to a conjugated group, and R3 is a hydrogen (BDE˜76.0).For a sixteenth example, R1 includes a phenyl ring attached directly toC1, R2 includes a C═N double bond with its N end directly attached toC1, and the carbon end of the C═N double bond is directly bonded to twobenzene rings, and R3 is a hydrogen. It has been found that C1 whenattached to the N end of the C═N double bond, the oxidizable additivehas specially high reactivity. Therefore, oxidizable additives havingthis functional group may be particularly useful for, for example, lowtemperature packaging (e.g. refrigerated temperature), packagingrequiring rapid removal of oxygen inside the packaging container,packaging requiring zero or near zero amount of residual level (oringression) of oxygen. Conversely, oxidizable additives having thisfunctional group may require special handling during the processing ofthe composition to ensure the effectiveness is not substantiallyaffected by the processing. For example, a liquid carrier may benecessary. For a seventeenth example, R1 includes a naphthalene ring, R2includes an ester group attached to C1 with the carbonyl carbon atom,and R3 is a hydrogen (BDE=84.9). For an eighteenth example, R1 includesan anthraquinone attached to C1 with one of its peripheral carbon atoms,and R2 includes an ester group attached to C1 with the non-carbonyloxygen atom, R3 is hydrogen (BDE<86.5). For a nineteenth example, R1includes a carbonyl group with the carbonyl carbon atom attacheddirectly to C1, and R2 includes a C≡C triple bond. For a twentiethexample, R1 includes a C═C double bond directly attached to C1, R2includes a carboxylic acid or ester group with its carbonyl carbonattached to C1, and R3 is a hydrogen. For a twenty-first example, R1includes a benzene ring directly attached to C1, R2 includes cyano groupdirectly attached to C1, and R3 includes a methyl group (BDE<82.0). Fora twenty-second example, R1 includes a C═C double bond directly attachedto C1, R2 includes a nitrogen atom directly connected to C1 and alsodirectly to two allylic carbon (BDE˜84.7). For a twenty-third example,R1 includes a C≡C triple bond directly attached to C1, R2 includes aphosphorous atom directly connected to C1 and also directly to anallylic carbon, and R3 is a hydrogen. For a twenty-fourth example, R1includes a phenyl directly connected to C1, R2 includes N(═O) directlyconnected to C1 with its nitrogen atom, wherein the nitrogen atom alsodirectly connects to two benzyl carbon atoms, and R3 is a hydrogen. In atwenty-fifth example, R1 includes a naphthalene directly connected toC1, R2 includes P(═O) directly connected to C1 with its phosphorousatom, wherein the phosphorous atom also directly connects to two benzylcarbon atoms, and R3 is a hydrogen. For a twenty-sixth example, R1 andR2 both includes —CN directly connected to C1, and R3 is a methyl group.

In a second aspect of the first embodiment, R1 includes a—X(═Y)-A^(H)-group, wherein A^(H) is a heteroatom having a free lonepair and directly attached to C1, X selected from an N, P, and CR^(a),and Y selected from selected from an O, S, NR^(a), PR^(a), andCR^(b)R^(c), independent of the identity of X, wherein R^(a), R^(b),R^(c) is each independently selected from H, an organic residue and anorganometallic residue; R2 includes a mesomeric group directly connectedto C1 via an atom of sp² hybridization, sp hybridization or with a freelone pair directed connected to or in close proximity to and inelectronic communication with C1 or a hydrogen atom attached to C1; andR3 is selected from a hydrogen (H), an organic residue and anorganometallic residue.

The following description details options for R1 and options for R2independent of each other's selection. Each such R1 option may becombined with each such R2 option unless stated otherwise or chemicallyimpossible, such as when valence cannot be satisfied, or when thecombination leads to unstable compound.

In a first sub-aspect of the second aspect with respect to R1, R1includes a carboxylate group connected to C1 via the non-carbonyloxygen. In a second sub-aspect of the second aspect with respect to R1,R1 includes an amide group connected to C1 via the nitrogen atom. In athird sub-aspect of the second aspect with respect to R1, R1 includes asulfonamide, a sulfinamide or a sulfenamide group connected to C1 viathe nitrogen atom. In a fourth sub-aspect of the second aspect withrespect to R1, R1 includes a sulfonate, a sulfinate or a sulfenate groupconnected to C1 via one of the oxygen atoms. In a fifth sub-aspect ofthe second aspect with respect to R1, R1 includes a phosphate, aphosphonate, or a phosphinate, connected to C1 via one of the oxygenatoms. In a sixth sub-aspect of the second aspect with respect to R1, R1includes a phosphamide, a phosphoramide, or a phosphiramide groupconnected to C1 via the nitrogen atom.

In a first sub-aspect of the second aspect with respect to R2, R2includes a conjugated group. For example, R2 includes any of theconjugated groups described above in the first aspect. For a firstexample, R2 includes a benzene ring directly attached to C1 when R1includes an amide group directly attached to C1 via the nitrogen atom.For a second example, R2 includes a conjugated group other than abenzene ring directly attached to C1 when R1 includes an amide groupdirectly attached to C1 via the nitrogen atom. For a third example, R2includes a benzene group when R1 does not include an amide groupdirectly attached to C1 via the nitrogen atom.

In a second sub-aspect of the second aspect with respect to R2, R2includes an atom A2 in proximity to and electronic communication withthe C1, the atom selected from an oxygen, a sulfur, a phosphorous, and anitrogen. For a first example, R2 includes a polyether fragment or apolyalkyleneglycol fragment having a carbon chain of 2 to 10 carbonatoms, wherein A2 is oxygen, not directly connected to but in proximityto and electronic communication with C1. For a second example, R2includes a tetrahydrofurfuryl group attached directly to C1 with acarbon atom next to the tetrahydrofurfuryl oxygen. For other examples,R2 is other than those described in the first two examples. For a thirdexample, R2 includes a polyether fragment or a polyalkyleneglycolfragment having a carbon chain of 11 or more carbon atoms wherein thefragment has an oxygen atom (A2) within a direct point-to-point distanceof approximately four C—O single bond distance away from C1. For afourth example, R2 includes one or more oxygen atoms wherein at leastone oxygen atom (A2) is within a direct point-to-point distance of threetypical C—O single bond distances from C1. For a fifth example, R2includes a polybutylene glycol fragment with at least one oxygen atom(A2) within a direct point-to-point distance of three typical C—O singlebond distances from C1. For other examples, R2 includes otherheteroatoms. For a sixth example, R2 includes a polyamine fragment witha nitrogen atom (A2) within a direct point-to-point distance of threetypical C—N single bond distances from C1. For a seventh example, R2includes a polyamine fragment with a nitrogen atom (A2) within a directpoint-to-point distance of three typical H—N single bond distances fromthe closer hydrogen atom attached to C1. For an eighth example, R2includes a etheramine (e.g. polyetheramine) fragment with a heteroatom(A2) within a direct distance of three typical H-A2 single bonddistances from the closer hydrogen atom attached to C1.

Representative examples of the present aspect may be understood inreference to the following examples of specific R1, R2, and R3. For afirst example, R1 is a benzoate connected to C1 via the non-carbonyloxygen atom; R2 is a polyether fragment or a polyalkyleneglycol fragmenthaving a carbon chain of 11 carbon atoms wherein the fragment has anoxygen atom (A2) within a direct point-to-point distance ofapproximately four C—O single bond distance away from C1; and R3 ishydrogen. BDE=For a second example, R1 is a benzamide connected to C1via the nitrogen atom; R2 is a polyamine fragment having a nitrogen atomwithin a direct point-to-point distance of approximately three typicalN—H single bond distance from a hydrogen atom attached to C1; and R3 ishydrogen. For a third example, R1 is an adipamide connected to C1 viaone of its nitrogen atoms, R2 is a tetrahydrofurfuryl group attacheddirectly to C1 via a carbon atom next to the tetrahydrofurfuryl oxygen;and R3 is a methyl group.

In a third aspect of the first embodiment, R1 includes a conjugatedsystem with connected carbons each with a sp2 hybridization pattern, R2and R3 each independently selected from a hydrogen, an organic residueand an organometallic residue, wherein the conjugated system issubstituted with R4.

The following description details options for R1 and options for R4independent of each other's selection. Each such R1 option may becombined with each such R4 option unless stated otherwise or chemicallyimpossible, such as when valence cannot be satisfied, or when thecombination leads to unstable compound.

In a first sub-aspect of the third aspect, the substituent R4 extendsthe conjugation of the conjugated system of R1. When the substituent isof an electron-withdrawing nature, R4 is preferably attached to theortho- or para-position of an aromatic ring relative to C1, or an evennumber of bonds away from C1 for better extension of conjugation.Alternatively, electron-withdrawing R4 may be attached to a positionwith an odd number of bonds away from C1 for linear 1,3-butadiene typeconjugation systems. For a first example, R1 includes a conjugationsystem of a C═C double bond directly connected to C1 and thesubstitution R4 is a second C═C double bond such that the conjugatedsystem is extended onto the substitution. For a second example, R1includes a conjugated system of a benzene ring directly connected to C1,and the substitution R4 includes a 1,3-butadiene which bonds to twoneighboring members of the benzene ring with its two end carbons,thereby forming a naphthalene ring. There may be additionalsubstitutions on the extended conjugation system. For a third example,R1 includes a conjugated system of a benzene ring directly connected toC1 and R4 includes a C═C double bond such that the conjugated system isextended onto the substitution. For a fourth example, R1 includes aconjugated system of a benzene ring and R4 includes a group selectedfrom —CN and —NO on para- or ortho-position of a benzene ring relativeto C1, such that the conjugated system is extended onto thesubstitution.

In a second sub-aspect of the third aspect, R1 includes a conjugatedsystem of an aromatic ring and the substituent R4 is selected from (1)an inductive electron-donating group directly attached to the aromaticring, (2) a mesomeric electron-donating group directly attached to ameta-position of the aromatic ring relative to the C1, (3) a mesomericelectron-donating group directly attached to a para- or ortho-positionof the aromatic ring relative to the C1, and (4) an inductiveelectron-donating group in proximity and electronic communication withC1 or an hydrogen atom attached to C1, but not directly bonded to thearomatic ring.

Representative examples of the present aspect may be understood inreference to the following examples. For a first example, the aromaticring is a benzene ring attached directly to Cl, and R1 includes aninductive electron-donating group of a B(OH)₃— group attached to thebenzene ring. The inductive electron-donating group does not have asubstantial mesomeric EDG effect. For a second example, the aromaticring is a benzene ring attached directly to C1, and R1 includes aninductive electron-donating group of a —C(═O)O⁻ group attached to themeta-position of the benzene ring relative to C1. For a third example,the aromatic ring is a benzene ring attached directly to C1, and R1includes a mesomeric electron-donating group of an amine group attachedto the meta-position of the benzene ring relative to C1. For a fourthexample, the aromatic ring is a benzene ring attached directly to C1,and R1 includes a mesomeric electron-donating group of alkoxide groupattached to the para- or ortho-position of the benzene ring relative toC1. For a fifth example, R1 includes an electron-donating group attachedto both the meso- and para-positions of the aromatic ring relative tothe C1 to form a ring. For a sixth example, R1 includes anelectron-donating group attached to both the meso- and para-positions ofthe aromatic ring relative to the C1 to form a ring, wherein theelectron-donating group is a predominantly inductive electron-donatinggroup. For a first instance, the electron-donating group attaches to thearomatic ring with two carbon atoms. For a second instance, theelectron-donating group is selected from —(CH₂)₃—, —(CH₂)₄—,—(CH₂)₅—,—(CH₂)₆— and derivatives thereof and attaches to the aromatic ring withtwo carbon atoms. For a third instance, the electron-donating group is aheteroatom derivative of one of —(CH₂)₃—, (CH₂)₄—,—(CH₂)₅—, and—(CH₂)₆—, and attaches to the aromatic ring with a heteroatom. For aneighth example, R1 includes an electron-donating group attached to boththe meso- and ortho-positions of the aromatic ring relative to the C1 toform a ring. In a ninth example, the electron-donating group attaches toboth the meso- and ortho-positions of the aromatic ring relative to theC1 to form a ring, wherein the electron-donating group is apredominantly inductive electron-donating group. For a first instance,the electron-donating group attaches to the aromatic ring with twocarbon atoms. For a second instance, the electron-donating group isselected from —(CH₂)₃—, —(CH₂)₄—,—(CH₂)₅—, —(CH₂)₆— and derivativesthereof and attaches to the aromatic ring with two carbon atoms. For athird instance, the electron-donating group is a heteroatom derivativeof one of —(CH₂)₃—, —(CH₂)₄—,—(CH₂)₅—, and —(CH₂)₆—, and attaches to thearomatic ring with a heteroatom.

In a fourth aspect of the first embodiment, R1 is an electron donatinggroup, R2 is an electron withdrawing group, and R3 is selected from ahydrogen, an organic residue and an organometallic residue. It ispreferable, although not necessary, that R1, R2, and R3 do not assert astrong inductive electron-withdrawing effect. The following descriptiondetails options for R1 and options for R2 independent of each other'sselection. Each such R1 option may be combined with each such R2 optionunless stated otherwise or chemically impossible, such as when valencecannot be satisfied, or the combination leads to unstable compound.

In a first sub-aspect, R1 is a strong mesomeric electron-donating group,R2 is a strong mesomeric electron-withdrawing group, and R3 is selectedfrom a hydrogen, an organic residue and an organometallic residue. Forexample, R1 is selected from a phenoxide (—O⁻) group, an amine (—NR₂,—NHR, —NH₂) group, an ether (—OR) group, and a hydroxy (—OH) group; R2is selected from a cyano (CN) group, a triflyl (—SO₂CF₃) group, asulfonate (—SO₃H) group, a nitro (—NO₂) group.

In a second sub-aspect, at least one of R1 and R2 is not a strong-effectmesomeric electron-donating group, and R3 includes a conjugated groupattached to C1 via an atom of a hybridization pattern selected from sp2and sp. For example, R1 is a predominantly inductive electron-donatinggroup, R2 is a predominantly inductive electron-withdrawing group, orone of R1 and R2 is a weak to moderate effect group. More specifically,for a first example, R1 is selected from B(OH)₃—, (CH₂)₃—, (CH₂)₄—,(CH₂)₅— and derivatives thereof, R2 is a carboxylate (—COOR₄) groupattached to C1 with the carbonyl carbon, and R3 is a benzene or C═Cdouble bond directly attached to C1. For a second example, R1 isselected from thiolate anion (—S⁻) group, an oxide anion (—O⁻) group, anamine (—NR₂, —NHR, —NH₂) group, an ether (—OR) group, and a hydroxy(—OH) group, amide (—NHCOR) group, an ester (—OCOR) group, a sulfonamide(—NHS(═O)₂R) group, a styryl (—CH═CH—C₆H₅) group, a ferrocenyl group, atriphenylphosphine imide (—N═P(C₆H₅)₃) group, a thiol (—SH) group, aphosphonic dichloride (—P(═O)Cl₂) group, an isocyanate (—N═C═O) group,an alkyl groups, a methylenedioxy (—OCH₂—) group, a vinyl (—CH═CH₂)group, a trialkyltin (—Sn(CH₃)₃) group, a furyl group, a thienyl goup, atetramethylsilane (—CH₂—Si(CH₃)₃) group, and derivatives thereof; R2 isselected from a cyano (CN) group, a triflyl (—SO₂CF₃) group, a trihalidegroup (—CF₃, —CCl₃), a sulfonate (—SO₃H) group, a nitro (—NO₂) group, anitrosyl (—NO) group, an aldehyde (—CHO) group, a ketone (—COR) group, acarboxylic acid (—COOH or —COO⁻) group, an acyl chloride (—COCl) group,an esters (—COOR) group, and an amide (—CONH₂) group, a nitrogen cation(—N⁺≡N) group, an arsenic acid (As(O)(OH)₂ or AsO₃H⁻) group, asulfonamide (—S(═O)₂NHR, (—S(═O)₂NR₂) group, a trifluoromethyl (—CF₃)group, methylsulfinate (—SO₂(CH₃)) group, methylsulfenate (—SOCH₃)group, thiocyanate (—SCN) group, alkyne (—C≡CH) group, vinyl with strongelectron-withdrawing groups (e.g. —CH═CH—NO₂), a dialkyl phosphoryl(—P(═O)R₂) group, a dialkyl thiophosphoryl (—P(═S)R₂) group, adialkylphosphine (—PR₂) group, a tetramethylphosphonium (—P(CH₃)₄ ⁺)group, pyridyl groups, a benzoxazole group, a benzothiazolyl group, aconjugated group or hyperpolarizable atom directly bonded toperfluorinated alkyl groups, and derivatives thereof; and R3 is selectedfrom an aromatic group, an alkenyl group, and a alkynyl group.

Representative examples of the present aspect may be understood inreference to the following examples of specific R1, R2, and R3. For afirst example, R1 includes a —NH₂ attached directly to C1, R2 includes a—CN attached directly to C1, and R3 is a hydrogen. For a second example,R1 includes a fragment selected from an ether, a hydroxy, a thiol, athioether, and an amine fragment, each with the heteroatom directlyattached to C1, and R2 includes a carbonyl directly attached to C1. Forinstance, R1 includes a thiolate group (PhS- or PrS-) directly attachedto C1, R2 includes one of —C(O)-Ph, —C(O)—N-Ph, —C(O)—O-Ph, and R3 ishydrogen, wherein Ph represents phenyl group, and Pr represents a propylgroup. For a third example, R1 includes a —OH attached directly to C1,R2 includes a —COOH attached directly to C1, and R3 includes a C═Cattached directly to C1. For a fourth example, R1 includes a fragmentselected from a hydroxy group, an alkoxide group with the oxygen atomattached to C1, an amine group with the nitrogen atom attached to C1, R2includes a fragment selected from a carboxylic acid group, an estergroup each with the single bonded oxygen attached directly to C1 and anamide group with the single bonded nitrogen attached directly to C1, andR3 includes a benzene ring directly attached to C1. For a fifth example,R1 includes a C═C double bond directly attached to C1, R2 includes anelectron-withdrawing group, such as ammonium ions —N(CH₃)₃ ⁺, —NH₃ ⁺,and R3 is a hydrogen. For a sixth example, R1 includes an imido—N═C(CH₃)(OH), and R3 includes a —C═CH₂ group. For a seventh example, R1is a (Ar₂—CZ₁Z₂)(Ar₁—CZ₃Z₄)Q fragment wherein the Ar₁ and Ar₂ are eachindependently selected from an aryl and a heteroaryl which is eachindependently substituted with 0, 1, 2, or 3 groups independentlyselected from halogen, C1-C4 alkyl, and electron withdrawing groups andvalence is satisfied, Z1-Z4 each independently selected from hydrogen,halogen, C1-C4 alkyl, electronic withdrawing group, electronic donatinggroup, or collectively ═O; provided that at least one set of Z¹ and Z²are hydrogens; and Q is selected from N and P and directly bonds to C1;and R2 is a substituted phenyl group. For an eighth example, the R1 andR2 combination is other than the combination of the seventh example. Fora first instance, R1 includes (Al—CZ₁Z₂)(Al—CZ₃Z₄)Q, wherein Alrepresents a substituted or unsubstituted allyl group, Z₁-Z₄ areindependently selected from hydrogen, an organic residue and anorganometallic residue provided that at least one of Z₁-Z₄ is a hydrogenatom, and Q is selected from N and P; and R2 includes an allyl group.For a second instance, R1 includes (Ar₂—CZ₁Z₂)(Ar₁—CZ₃Z₄)Q fragmentwherein the Ar₁, Ar₂, Z₁-Z₄ are according to as described above for theseventh example, and Q is selected from a nitrosyl (—N═O) and aphosphoryl (—P═O) and directly bonds to C1; and R2 is a conjugatedgroup.

In a fifth aspect of the first embodiment, the structure as described inany one of the above aspects, wherein the structure further includes aring. In various situations, the structures including a ring may bepreferable due to various reasons. For example, if the oxidizationreaction involves cleavage of a single bond which is part of a ring, nomigratable product will be produced and cause complications with respectto health or safety. For another example, the C1 atom is part of a rigidring, wherein bonds involving C1 are not freely rotatable The rigidityof a ring minimizes the change of steric strain energy during theoxidation reaction which is beneficial towards increasing the reactivitytowards oxygen.

In a sixth aspect of the first embodiment, the structure as described inany one of the above aspects, wherein the structure is a polymeric.

In a seventh aspect of the first embodiment, the structure as describedin any one of the above aspects, wherein the structure is a dendrimeric.

In an eighth aspect of the first embodiment, the structure as describedin any one of the above aspects, wherein the structure is a host-guestcomplex.

In a ninth aspect of the first embodiment, the oxidizable additivefurther includes multiple coordinative sites and further includes ametal ion interacting with at least one of the multiple coordinativesites. In a first sub-aspect, the metal ion is redox-inert. In a secondsub-aspect, the metal ion is redox-active. In a third sub-aspect, themetal ion also serves as the oxidation catalyst.

In a tenth aspect of the first embodiment, the formulation furtherincludes a catalyst. The catalyst is described further in a latersection.

In an eleventh aspect of the first embodiment, the oxidizable additivehas an OI higher than approximately 100. In the tenth aspect of theinvention, the oxidizable additive has an OOI higher than approximately100.

In a twelfth aspect of the first embodiment, the oxidizable additivefurther includes a C—H bond having a homolytic BDE satisfying athreshold as described in the third embodiment later.

In a second embodiment of the present invention, the formulationincludes a discrete, oligomeric, or polymeric molecule that is selectedfrom an oxidizable additive and a precursor to the oxidizable additive,wherein said precursor is capable of being converted into the oxidizableadditive during processing or application of the formulation.

The oxidizable additive comprises a first organic or organometallicfragment selected from a first group consisted of formulae (I), (II),(III), (IV), and (V):

wherein at least one of R₁ and R₂ includes a fragment selected from thegroup consisted of formulae (A)-(D):

wherein Ar₁ may be any organic or organometallic aromatic substituent;R3 may be selected from hydrogen (H), an organic residue, and anorganometallic residue; X, Y, X₁, and Y₁ may each be independentlyselected from the group consisted of CR₀, SiR₀, N, P; Z, Q, Z₁, are eachindependently selected from the group consisted of O, S, NR₀, PR₀,wherein R₀ is selected from H, or any organic or organometallic residue;and C.G. represents a conjugated group as described above in the firstembodiment.

In a first aspect of the second embodiment, the structure includesformula (I), R₁ includes formula (A), and R₂ and R₃ are eachindependently selected from a hydrogen, an organic residue and anorganometallic residue. In a first sub-aspect, R₂ is selected frombenzene and naphthalene and R₂ has two identical substituents, Q is —NH—and Z is O. In a second sub-aspect, the combination of R₂, Q, and Z areother than that described for the first sub-aspect. For a first example,Ar₁ is selected from an organic and an organometallic aromaticsubstituent; Z and Q are each independently selected from the groupconsisted of O, NR₀, S, PR₀, wherein R₀, R₂ and R₃ are eachindependently selected from H, an organic residue, and an organometallicresidue. For a first instance, Z and Q are both oxygen, R₂ is hydrogen,and R₃ is hydroxy group (—OH). For a second instance, Z and Q are bothoxygen, R₂ is hydrogen, and R₃ is alkoxy group (—OR₀). For a thirdinstance, Z and Q are both oxygen, R₂ is alkyl group, and R₃ is alkoxygroup (—OR₀). For a fourth instance, Z is oxygen, Q is nitrogen, R₂ isan alkyl group, R₃ is hydrogen. For a second example, R₂ is selectedfrom benzene and naphthalene, wherein R₂ has two identicalsubstitutions; Q is —NH— and Z is oxygen (O). For a third example, R₂ isan aromatic ring other than benzene or naphthalene. For a fourthexample, R₂ is selected from benzene or naphthalene, and Ar₁ is otherthan a benzene group.

In a second aspect of the second embodiment, the structure includesformula (I), R₁ is selected from the group consisted of formulae(B)-(D), and R₂ and R₃ are each independently selected from a hydrogen,an organic residue and an organometallic residue. For a first example,R₁ includes formula (C), wherein both Z₁ and X₁ are ═CH₂, Z is oxygen(O), Q is —NH— and R₂ is hydrogen. For a second example, R₁ includesformula (C), wherein X is ═CR₀— (R₀ is —COOH), Z₁ is —CH₂—, both Z and Qare oxygen (O), and R₂ is hydrogen. For a third example, R₁ includesformula (C), wherein X is ═CR₀— (R₀ is —COOR₄), Z₁ is —CH₂—, both Z andQ are oxygen (O), and both R₂ and R₄ include alkyl groups.

In a third aspect of the second embodiment, the structure includesformula (I), R₁ and R₃ are each independently selected from H, anorganic residue and an organometallic residue; R₂ includes formula (A),Z and Q are each independently selected from the group consisted of O,NR₀, S, PR₀, CR₀R₄, wherein R₀ and R₄ are each independently selectedfrom H, an organic residue and an organometallic residue; wherein Q mayinclude nitrogen directly connected to C₂ only either when Z is notoxygen, or when Ar₁ is selected from an organic aromatic group and anorganometallic aromatic group which does not include a benzene directlyconnected to C2.

In a fourth aspect of the second embodiment, the structure includesformula (I), R₁ and R₃ are each independently selected from H, anorganic residue and an organometallic residue; R₂ includes formula (C),Z and Q are each independently selected from the group consisted of O,NR₀, S, PR₀, CR₀R₄, wherein R₀ and R₄ are each independently selectedfrom H, an organic residue and an organometallic residue; wherein Q mayinclude nitrogen directly connected to C2 only either when either Z isnot oxygen, or when Z₁═X₁ is not a C═C double bond.

In a fifth aspect of the second embodiment, the structure includesformula (I), R₁ and R₃ are each independently selected from H, anorganic residue and an organometallic residue; R2 includes a formula(A), Z and Q are each independently selected from the group consisted ofO, NR₀, S, PR₀, CR₀R₄, wherein Ar₁ is selected from an organic aromaticgroup and an organometallic aromatic group and does not include twoidentical substitutions, R₀ and R₄ are each independently selected froma hydrogen, an organic residue and an organometallic residue. Forexample, Q is —NR₀—, Z is oxygen.

In a sixth aspect of the second embodiment, the structure includesformula (I), R₁ and R₃ are each independently selected from H, anorganic residue and an organometallic residue; R₂ includes a formula(C), Z, Z₁, and Q are each independently selected from the groupconsisted of O, NR₀, S, PR₀, CR₀R₄, X₁ is selected from the groupconsisted of CR₀, SiR₀, N, P, wherein R₀ and R₄ are each independentlyselected from H, an organic residue and an organometallic residue. Forexample, Q is —NR₀—, Z is oxygen.

In a seventh aspect of the second embodiment, the structure includesformula (I), R₁ and R₃ are each independently selected from H, anorganic residue and an organometallic residue; R₂ includes formula (A),Z and Q are each independently selected from the group consisted of O,NR₀, S, PR₀, CR₀R₄; wherein R₁ does not include the group —C(═Z)-Q-R₂,and R₀ and R₄ are each independently selected from a hydrogen, anorganic residue and an organometallic residue. For example, Q is —NR₀—,Z is oxygen.

In an eighth aspect of the second embodiment, the structure includesformula (I), R₁ and R₃ are each independently selected from H, anorganic residue and an organometallic residue; R₂ includes formula (C),Z and Q are each independently selected from the group consisted of O,NR₀, S, PR₀, CR₀R₄; wherein R₁ includes the group —C(═Z)-Q-R₂, and R₀and R₄ are each independently selected from a hydrogen, an organicresidue and an organometallic residue. For example, Q is —NR₀—, Z isoxygen.

In a ninth aspect of the second embodiment, the structure includesformula (I), R₁ and R₃ are each independently selected from H, anorganic residue and an organometallic residue; R₂ includes one offormulae (B) and (D), Z and Q are each independently selected from thegroup consisted of O, NR₀, S, PR₀, CR₀R₄, wherein R₀ and R₄ are eachindependently selected from H, an organic residue and an organometallicresidue.

In a tenth aspect of the second embodiment, the structure includesformula (II), R1 includes one of formulae (A), (B), and (D). For a firstexample, X is N, Y is CR₀, wherein R0 is selected from a hydrogen, anorganic residue and an organometallic residue, R1 includes formula (A).For a second example, X, Y, R0 are according to the first example, andR2 includes a conjugated group attached to Y with an atom of sp²hybridization, and R1 includes formula (B). For a third example, X isCR₀, Y is CR₅, wherein at least one of R₂ and R₅ is a conjugated group.For a fourth example, X is CR₀, Y is CR₅, wherein R₂ and R₅ collectivelyforms a ring. For a fifth example, X is N, Y is CR₅, wherein R₂ and R₅each includes a C═C double bond and collectively forms a ring. For asixth example, X is N, Y is CR₅, wherein R₂ and R₅ each includes abenzene ring and collectively forms a ring between the two benzenerings.

In an eleventh aspect of the second embodiment, the structure includesformula (II), R₁ includes formula (C). For a first example, X1, Z1, X,and Y all include a carbon atom. For a second example, at least one ofX1, Z1, X, and Y does not a carbon atom. For a third example, at leastone of X1, Z1, X, and Y includes a nitrogen (N) or a phosphorous (P).

In a twelfth aspect of the second embodiment, the structure includesformula (III), R₁ and R₂ are each independently selected from formulae(A)-(D). In a first sub-aspect, R₁ and R₂ are both represented byformula (C) wherein the X₁═Z₁ groups of both R₁ and R₂ are C═C groups atthe same time. In a second sub-aspect, R₁ and R₂ are not according tothe first sub-aspect as described above. In a third sub-aspect, R₁ andR₂ are both represented by formula (C) and are carbonyls, wherein Z₁ isoxygen for both R₁ and R₂; X₁ is CR₀ for both R₁ and R₂, wherein R₀ forR₁ and R₂ are each independently selected from any non-hydrogen organicradicals and organometallic residues. In a fourth sub-aspect, R₁ and R₂are both represented by formula (C) and are carbonyls, wherein the Z₁ isoxygen for both R₁ and R₂; X₁ is CR₀ for both R₁ and R₂, and R₃ for R₁and R₂ are each independently selected from an EDG, an EWG, a conjugatedgroup, and an organometallic group. In a fifth sub-aspect, R₁ and R₂ areboth represented by formula (C) and are carbonyls, wherein the Z₁ isoxygen for both R₁ and R₂; X₁ is CR₀ for both R₁ and R₂, and R₃ for oneof R₁ and R₂ is selected from an EDG, an EWG, a conjugated group, and anorganometallic group, and R₃ for the other of R₁ and R₂ is hydrogen, andeither R₀ for R₂ does not include R₃ for R₁ or R₀ for R₁ does notinclude R₃ for R₂. In a sixth sub-aspect, R₁ and R₂ both represented byformula (A) and both includes a benzyl group directly attached to eachother. In a seventh sub-aspect, R₁ is represented by formula (C) and R₂is represented by formula (D). For example, R₁ includes an allyl groupwherein Z₁═X₁ is C═C double bond; R₂ includes an amide group wherein X₁is CR₀, Z₁ is oxygen, Q is nitrogen.

In a thirteenth aspect of the second embodiment, the structure includesformula (IV), wherein E is any atom with a lone pair or any conjugatedgroup which connects to R₁ with a sp2 or sp hybridized atom; wherein R₁and R₂ are each independently selected from formulae (A)-(D). In onesub-aspect, E is selected from NR₅ and PR₅, wherein R₅ is selected fromformulae (A)-(D) independent of the choice of R₁ and R₂, wherein atleast one of R₁, R₂ and R₅ is represented by formula (A) and includes abenzyl group directly attached to E. In a second sub-aspect, both R₁ andR₂ are benzyl group, E is not NH, NR₁, NR₂, PH, PR₁, or PR₂, and E isdirectly attached to a third benzyl group. For first example, both R₁and R₂ are benzyl group, E is —P(═O)R₅ or —N(═O)R₅ and is directlyattached to the third benzyl group, wherein R₅ is selected from formulae(A)-(D) independent of the choice of R₁ and R₂. For a second example, Eis selected from NR₅ and PR₅, E is not directly attached to a benzyliccarbon of a benzyl group, and at least one of R₁ and R₂ includes anallyl group, wherein R₅ is selected from formulae (A)-(D) independent ofthe choice of R₁ and R₂.

In a fourteenth aspect of the second embodiment, the structure includesformula (V) wherein C.G. represents a conjugated group as describedabove. In a first example, R₁ includes formula (A) and C.G. includes abenzene group attached directly to R₁. In a second example, R₁ includesformula (B) and C.G. includes a double bond attached directly to R₁. Ina third example, R₁ includes formula (C) and C.G. includes an aromaticgroup attached directly to R₁ with one of the members of the aromaticring. In a fourth example, R₁ includes formula (D) and C.G. includes aC═C double bond directly attached to

In a fifteenth aspect of the second embodiment, the structure asdescribed in any one of the above aspects, wherein the structure furtherincludes a ring. In various situations, the structures including a ringmay be preferable due to various reasons as described above.

In a sixteenth aspect of the second embodiment, the structure asdescribed in any one of the above aspects, wherein the structure ispolymeric.

In a seventeenth aspect of the second embodiment, the structure asdescribed in any one of the above aspects, wherein the structure isdendrimeric.

In an eighteenth aspect of the second embodiment, the structure asdescribed in any one of the above aspects, wherein the structure is ahost-guest complex.

In a nineteenth aspect of the second embodiment, the oxidizable additivefurther includes multiple coordinative sites and further includes ametal ion interacting with at least one of the multiple coordinativesites. In a first sub-aspect, the metal ion is redox-inert. In a secondsub-aspect, the metal ion is redox-active. In a third sub-aspect, themetal ion also serves as the oxidation catalyst.

In a twentieth aspect of the second embodiment, the formulation furtherincludes a catalyst. The catalyst is described further in a latersection.

In a twenty-first aspect of the second embodiment, the oxidizableadditive has an OI higher than approximately 100. In the tenth aspect ofthe invention, the oxidizable additive has an OOI higher thanapproximately 100.

In a twenty-second aspect of the second embodiment, the oxidizableadditive further includes a C—H bond having a homolytic BDE satisfying athreshold as described in the third embodiment later. It is understoodthat the oxygen scavenging activity is directly correlated with thehomolytic BDE of the weakest bond of the molecule, which, may beaffected by the presence of additional components of the composition, asdescribed in more details below. Generally, the lower the BDE is, theweaker the bond is, and the more active the molecule would be in oxygenscavenging.

In a third embodiment, the oxidizable additive includes a C—H bond of ahomolytic bond dissociation energy lower than a certain threshold. Inother words, when there exists a C—H bond of a homolytic bonddissociation energy less than the threshold, the material may be anoxidizable additive. The threshold depends on the application. For rigidor semi-rigid polyethylene terephthalate container applications, forexample, the threshold is approximately 87.5 kcal/mol. If the BDE is toohigh, for example, higher than approximately 87.5 kcal/mol, the activityof the oxygen scavenger may not be sufficient for the application. Otherapplications may require a threshold higher or lower than this number.Furthermore, this threshold may be increased or lowered by the presenceof certain ingredient. For example, if there exists an oxidationcatalyst (e.g. Co²⁺) and the oxidizable additive includes a coordinatingsite, this threshold may be pushed higher to, for example, about 93kcal/mol, or in some cases about 98 kcal/mol. Similar effects arepresent for other threshold values described below and/or for otherapplications. Conversely, if there exists no oxidation catalyst, thethreshold may be substantially lowered to, such as below 77 kcal/mol. Ifthe BDE is too low, the oxidizable additive may not be stable enough towithstand processing condition.

We have compiled a large database of information on BDEs, a portion ofwhich listed below. The molecules are named either by their chemicalname, conventional name, or chemical structures representation. Thechemical structures, in this paragraph, may include abbreviations, suchas: Bn or Ph means phenyl; By means benzyl; Al means allyl; Tn meanstoluene; DB means CH₂═CH—, B(OH)₃ means the boric acid; Py meanspyridine; C3 means —CH₂—CH₂—CH₂— that forms a ring with other fragmentof the molecule; or any other abbreviations recognizable by a person ofskill in the art. Allyl˜87.2; Toluene˜90.0; Asorbic Acid˜85.1; Benzene(reported)˜113.0; Phenol (O—H) (reported)˜88.0; (t-Bu)2Phenol (O—H)(reported)˜82.5; benzylphthalamide˜88.0; polybutadiene˜85.7;N-benzylbenzamide˜81.4; N-benzylbenzamide ˜82.1; dibenzyl urea˜88.5;Mandelic Acid˜75.5; Mandelide˜79.1; Polymandelide˜86.1; PLA˜94.1;PGA˜91.1; dimethylbenzylamine˜84.7; semiquinone-benzyl aminecondensed˜59.8; benzylbenzilidene˜76.0; N-methylbenzamide˜93.3;N-C5NH10-benzamide˜92.1; N-dimethylbenzamide˜93.5;methylPhenylacetate˜84.9; methylPhenylacetamide˜85.7;methylPhenylacetamide˜85.4; benzyl benzoate˜86.5; dibenzylmethane˜84.7;N-allyldimethylimine˜73.1; C3 dicarboxylic acid˜93.0;benzylacetate˜85.0; tetrahydrofuran˜93.3; tetrahydrofuran˜C1-acetate(C1—H)˜97.1; 2-butyne˜89.6; C˜H in PMHS monomer˜100.5; Si—H inPMHS˜94.7; Si˜H in PMHS (Si3 oligomer)˜95.8; CN-substituted PMHS˜98.5;NH2-substituted PMHS˜96.3; methyl benzoate˜97.5; itaconic acid˜87.8;BCMOMe (reported)˜81.0; BCE (reported)˜88.0; BCN (reported)˜93.0; CH4(reported)˜105.0; By-SPh (reported)˜84.0; Pyrrolidine˜92.1;N,N-dimethylpyrrolidine˜106.7; Tn-p-NMe+˜91.9; N-methylpyrole˜93.4;N,N-dimethylpyrole˜108.0; benzylchloride˜86.3; benzylfluoride˜88.2;nitrosomethylbenzene˜65.2; nitrosomethylbenzene˜64.2;Phosphorylmethylbenzene˜93.5; dimethylbenzylamine N-oxide˜94.5;dimethylbenzylphophine oxide˜89.5; N-benzylformamide˜82.5;methylbenzylsulfide˜83.2; methylbenzylether˜89.1; methylbenzylether(method 2)˜88.1; Phenylacetylene˜79.9; Phenylacetonitrile˜82.0;(Nitromethyl)benzene˜88.5; dimethylbenzylphosphine˜87.8;Benzyltrimethylammonium˜96.5; benzylammonium˜94.0;Phenylacetaldehyde˜83.2; 3-Butenoic acid˜80.7; 2-hydroxy-3-Butenoicacid˜74.7; hydroxyl allylformate˜84.6; 1,4-pentyldiene˜73.2;hydroxylallylalcohol˜83.1; allylalcohol˜79.6; allylammonium˜86.6;trimethylallylammonium˜89.7; 4,4-difluoro-1-butene˜86.1;4-fluoro-1-butene˜85.1; 3-Butenenitrile˜79.2;4,4,4-trifluoro-1-butene˜87.5; N-allylimine˜75.5; N-allylimine(conformation 2)˜74.3; 3-nitroso-1-propylene˜63.7;3-nitro-1-propylene˜83.0; allyl acetylene˜76.6; Pyridine-p-CH3˜91.7;CH3C(═)ONCH2—CN˜83.4; HOC(═O)—CH2-CN˜90.0; HC(═O)OCH2—C(═O)—OH˜90.9;CH3C(═O)CCH2CH2OCH3˜97.4; NH2—CH2—CN˜81.3; NH2—CH2—OC(═O)H˜94.6;NH2-CH2-NH2˜93.2; CN—CH2—CN˜87.0; CF3—CH2-CF3˜106.7; Bn-C(═O)O-Me˜97.5;Me-C(═O)O-Me˜98.3; MeC(═O)NMe˜92.2; tetrahydrofuran-C1-acetate(furan-H)˜92.5; Tn-o-COOH˜89.7; Tn-m-CN˜91.3; Tn-m-CC˜90.5;Tn-m-N+≡N˜93.3; Tn-m-OH˜66.5; ˜90.6; ˜89.3; Tn-m-O—˜87.9; Tn-m-NO˜108.8;˜90.0; ˜110.4; Tn-m-NH2˜89.6; Tn-m-N3˜90.4; Tn-m-NH3+˜92.0; Tn-m-F˜90.6;Tn-m-NO2˜90.8; Tn-m-C═CH2˜89.5; Tn-m-B(OH)3˜87.1; Tn-mp-C4˜88.8;Tn-mp-C3˜90.1; TnmCOO—˜88.4; Tn-o,p-CN2˜89.5; Tn-CN˜89.3; Tn-p-OH˜89.8;Tn-p-NO2˜90.3; Tn-p-NO˜90.9; Tn-p-C═CH2˜88.2; Tn-p-OMe˜88.7;Tn-p-NMe3+˜91.9; Tn-p-NH3+˜91.4; Tn-p-B(OH)3˜86.5; Tn-p-COOH˜90.3;Tn-p-COOH (reported)˜89.8; Tn-p-NMe2˜85.8; Tn-p-NMe2 (reported)-88.5;Indane (benzylic C—H)˜87.7; Tn-p-C(═O)Me˜88.0; Tn-o,p-COOH2˜89.5;Tn-o-NO˜89.1; Benzyl-B(OH)3-CF3˜94.1; semiquinone-benzyl amine condensed(method 2)˜61.5; N-benzylbenzamide (method 2)˜80.3; mandelic acid(method 2)˜74.5; benzylbenzilidene (method 2)˜72.6; Tn-m,p-Me2˜89.3;Tn-m,p-Et2˜90.2; benzylbenzoate (method 2)˜85.4; Toluene˜89.1;Ph-OCH2—H˜97.6; DB-OCH2—H˜98.6; CH3—C(═O)OCH2CH2OCH3˜93.1; Al—O—Al˜79.7;TnNH2˜89.1; By-OH˜83.5; By-B(OH)3˜89.1; By-CF3˜92.4; Pyd-o-CH3˜91.7;Pyd-m-CH3˜90.8; Pyd-p-CH3˜91.6; CH2═N—CH3˜87.9; NH═CH—CH3˜91.0;NH═CH—CH2—NH2˜77.9; CH2═CH—CH═CH2—CH2—H˜80.3;NH2—CH═CH—CH═CH2—CH2—H˜77.8; CH2═C(NH2)—CH═CH2—CH2—H˜81.1;CN—CH═CH—CH═CH2—CH2—H˜78.6; CH2═C(CN)—CH═CH2—CH2—H˜81.0;B(OH3)—CH═CH—CH═CH2—CH2—H˜76.4; CH2═C(B(OH)3)—CH═CH2—CH2—H˜80.0;Tn-m-CF3˜91.4; Tn-p-CF3˜90.4; (HC(═O)CH2)2˜91.2; B(OH)3—CH2—CHF2˜101.1;B(OH)3—CH3˜100.2; CH3—CHF2˜105.2; B(OH)3—CH2—CN˜93.9; NH2—CH2—CHF2˜94.0;NH2—CH3˜92.8; CH3—CN˜95.7; CH4˜104.8; CH3COOH˜98.2; CH3OCOH˜99.3;DB-pk˜92.3; HC(═O)CH2—H˜94.7; BnC(═O)CH2—H˜95.7; DBC(═O)CH2—H˜94.9;NH2C(═O)CH2—H˜98.3; CNC(═O)CH2—H˜94.5; C(═O)-DB˜77.4; CO—NH2˜77.2;dihydrophthalimide˜80.9; polybutadiene (different C—H)˜83.7;dihydrophthalimide (method 2)˜79.7.

In a first aspect, the oxidizable additive includes a C—H bond of a bonddissociation energy lower than approximately 87.5 kcal/mol, wherein theC—H bond is selected from a benzylic C—H attached to the nitrogen atomof an amide functional group, a benzylic C—H ortho- or para- to anelectron-donating group, an allylic C—H attached to the nitrogen atom ofan amide functional group, an allylic C—H attached to another allyliccarbon, and a benzoate polyglycol ester C—H that is directly attached tothe ester group and in proximity of a transition metal catalyst.

In a first sub-aspect, the oxidizable additive is one according to oneof the first two embodiments as described above. In a second sub-aspect,the oxidizable additive includes a benzylic C—H of a bond dissociationenergy between approximately 87.5 kcal/mol and 83.0 kcal/mol, such asthose according to one of the first two embodiments as described above.In a third sub-aspect, the oxidizable additive includes a benzylic C—Hof a bond dissociation energy between approximately 83.0 kcal/mol and79.0 kcal/mol, such as those according to one of the first twoembodiments as described above. In a fourth sub-aspect, the oxidizableadditive includes a benzylic C—H of a bond dissociation energy lowerthan approximately 79.0 kcal/mol, such as those according to one of thefirst two embodiments as described above. In a fifth sub-aspect, theoxidizable additive includes an allylic C—H of a bond dissociationenergy between approximately 87.5 kcal/mol and 84.0 kcal/mol, such asthose according to one of the first two embodiments as described above.In a sixth sub-aspect, the oxidizable additive includes an allylic C—Hof a bond dissociation energy between approximately 84.0 kcal/mol and82.5 kcal/mol, such as those according to one of the first twoembodiments as described above. In a seventh sub-aspect, the oxidizableadditive includes an allylic C—H of a bond dissociation energy belowapproximately 82.5 kcal/mol, such as those according to one of the firsttwo embodiments as described above. In an eighth sub-aspect, theoxidizable additive includes a benzylic C—H ortho- or para- to anelectron-donating group and of a bond dissociation energy approximatelylower than approximately 87.5 kcal/mol, such as those according to oneof the first two embodiments as described above. In a ninth sub-aspect,the oxidizable additive includes a benzoate polyglycol ester C—H that isdirectly attached to the ester group and in proximity of a transitionmetal catalyst and of a bond dissociation energy lower thanapproximately 87.5 kcal/mol, such as those according to one of the firsttwo embodiments as described above.

In a second aspect, the oxidizable additive includes a C—H bond of abond dissociation energy lower than approximately 87.5 kcal/mol, whereinthe C—H bond is selected from other than a benzylic C—H attached to thenitrogen atom of an amide functional group, a benzylic C—H ortho- orpara- to an electron-donating group, an allylic C—H attached to thenitrogen atom of an amide functional group, an allylic C—H attached toanother allylic carbon, or a benzoate polyglycol ester C—H that isdirectly attached to the ester group and in proximity of a transitionmetal catalyst.

In a third aspect, the oxidizable additive includes a C—H bond that hasa bond dissociation energy lower than approximately 86 kcal/mol, such asthose according to one of the first two embodiments as described above.In a fourth aspect, the oxidizable additive includes a C—H bond that hasa bond dissociation energy lower than approximately 85 kcal/mol, such asthose according to one of the first two embodiments as described above.In a fifth aspect, the oxidizable additive includes a C—H bond that hasa bond dissociation energy lower than approximately 84 kcal/mol, such asthose according to one of the first two embodiments as described above.In a sixth aspect, the oxidizable additive includes a C—H bond that hasa bond dissociation energy lower than approximately 83 kcal/mol, such asthose according to one of the first two embodiments as described above.In a seventh aspect, the oxidizable additive includes a C—H bond thathas a bond dissociation energy lower than approximately 82 kcal/mol,such as those according to one of the first two embodiments as describedabove. In an eighth aspect, the oxidizable additive includes a C—H bondthat has a bond dissociation energy lower than approximately 81kcal/mol, such as those according to one of the first two embodiments asdescribed above. In a ninth aspect, the oxidizable additive includes aC—H bond that has a bond dissociation energy lower than approximately 80kcal/mol, such as those according to one of the first two embodiments asdescribed above. In a tenth aspect, the oxidizable additive includes aC—H bond that has a bond dissociation energy lower than approximately 79kcal/mol, such as those according to one of the first two embodiments asdescribed above. In an eleventh aspect, the oxidizable additive includesa C—H bond that has a bond dissociation energy lower than approximately78 kcal/mol, such as those according to one of the first two embodimentsas described above. In a twelfth aspect, the oxidizable additiveincludes a C—H bond that has a bond dissociation energy lower thanapproximately 75 kcal/mol, such as those according to one of the firsttwo embodiments as described above. In a thirteenth aspect, theoxidizable additive includes a C—H bond that has a bond dissociationenergy lower than approximately 72 kcal/mol, such as those according toone of the first two embodiments as described above. In a fourteenthaspect, the oxidizable additive includes a C—H bond that has a bonddissociation energy lower than approximately 69 kcal/mol, such as thoseaccording to one of the first two embodiments as described above. In afifteenth aspect, the oxidizable additive includes a C—H bond that has abond dissociation energy lower than approximately 66 kcal/mol, such asthose according to one of the first two embodiments as described above.In a sixteenth aspect, the oxidizable additive includes a C—H bond thathas a bond dissociation energy lower than approximately 63 kcal/mol,such as those according to one of the first two embodiments as describedabove. In a seventeenth aspect, the oxidizable additive includes a C—Hbond that has a bond dissociation energy lower than approximately 60kcal/mol, such as those according to one of the first two embodiments asdescribed above.

In an eighteenth aspect of the third embodiment, the formulation furtherincludes a catalyst. The catalyst is described further in a latersection.

In a fourth embodiment, the oxidizable additive includes a C—H bond, thehomolytic bond cleavage of which produces a radical including C. andwith an energy E_(g) over the energy of the oxidizable additive. Theenergy gap E_(g) is smaller than a certain threshold depending on theapplication. For rigid or semi-rigid polyethylene terephthalatecontainer applications, for example, the threshold is approximately 400kcal/mol. Other applications may require a threshold higher or lowerthan this number.

In a first aspect, the C—H bond is selected from a benzylic C—H attachedto the nitrogen atom of an amide functional group, a benzylic C—H ortho-or para- to an electron-donating group, an allylic C—H attached to thenitrogen atom of an amide functional group, an allylic C—H attached toanother allylic carbon, and a benzoate polyglycol ester C—H that isdirectly attached to the ester group and in proximity of a transitionmetal catalyst, wherein the energy gap E_(g) is smaller thanapproximately 400 kcal/mol.

In a first sub-aspect, the oxidizable additive is one according to oneof the first three embodiments as described above. In a secondsub-aspect, the C—H bond is a benzylic C—H wherein the energy gap E_(g)is smaller than approximately 400 kcal/mol but more than approximately396 kcal/mol, such as those according to one of the first threeembodiments as described above. In a third sub-aspect, the C—H bond is abenzylic C—H wherein the energy gap E_(g) is smaller than approximately396 kcal/mol but more than approximately 392 kcal/mol, such as thoseaccording to one of the first three embodiments as described above. In afourth sub-aspect, the C—H bond is a benzylic C—H wherein the energy gapE_(g) is smaller than approximately 392 kcal/mol, such as thoseaccording to one of the first three embodiments as described above.

In a fifth sub-aspect, C—H is an allylic C—H wherein the energy gapE_(g) is smaller than approximately 400 kcal/mol but more thanapproximately 397 kcal/mol, such as those according to one of the firstthree embodiments as described above. In a sixth sub-aspect, the C—Hbond is an allylic C—H wherein the energy gap E_(g) is smaller thanapproximately 397 kcal/mol but more than approximately 395 kcal/mol,such as those according to one of the first three embodiments asdescribed above. In a seventh sub-aspect, the C—H bond is an allylic C—Hwherein the energy gap E_(g) is smaller than approximately 395 kcal/mol,such as those according to one of the first three embodiments asdescribed above. In an eighth sub-aspect, the C—H bond is a benzylic C—Hortho- or para- to an electron-donating group wherein the energy gapE_(g) is smaller than approximately 400 kcal/mol, such as thoseaccording to one of the first three embodiments as described above. In aninth sub-aspect, the C—H bond is a benzoate polyglycol ester C—H thatis directly attached to the ester group and in proximity of a transitionmetal catalyst wherein the energy gap E_(g) is smaller thanapproximately 400 kcal/mol, such as those according to one of the firstthree embodiments as described above.

In a second aspect, the C—H bond is selected from other than a benzylicC—H attached to the nitrogen atom of an amide functional group, abenzylic C—H ortho- or para- to an electron-donating group, an allylicC—H attached to the nitrogen atom of an amide functional group, anallylic C—H attached to another allylic carbon, or a benzoate polyglycolester C—H that is directly attached to the ester group and in proximityof a transition metal catalyst, wherein the energy gap E_(g) is smallerthan approximately 400 kcal/mol.

In a third aspect, the energy gap E_(g) is less than approximately 399kcal/mol, such as those according to one of the first three embodimentsas described above. In a fourth aspect, the energy gap E_(g) is lessthan approximately 398 kcal/mol, such as those according to one of thefirst three embodiments as described above. In a fifth aspect, theenergy gap E_(g) is less than approximately 397 kcal/mol, such as thoseaccording to one of the first three embodiments as described above. In asixth aspect, the energy gap E_(g) is less than approximately 396kcal/mol, such as those according to one of the first three embodimentsas described above. In a seventh aspect, the energy gap E_(g) is lessthan approximately 395 kcal/mol, such as those according to one of thefirst three embodiments as described above. In an eighth aspect, theenergy gap E_(g) is less than approximately 394 kcal/mol, such as thoseaccording to one of the first three embodiments as described above. In aninth aspect, the energy gap E_(g) is less than approximately 393kcal/mol, such as those according to one of the first three embodimentsas described above. In a tenth aspect, the energy gap E_(g) is less thanapproximately 392 kcal/mol, such as those according to one of the firstthree embodiments as described above. In an eleventh aspect, the energygap E_(g) is less than approximately 390 kcal/mol, such as thoseaccording to one of the first three embodiments as described above. In atwelfth aspect, the energy gap E_(g) is less than approximately 388kcal/mol, such as those according to one of the first three embodimentsas described above. In a thirteenth aspect, the energy gap E_(g) is lessthan approximately 385 kcal/mol, such as those according to one of thefirst three embodiments as described above. In a fourteenth aspect, theenergy gap E_(g) is less than approximately 382 kcal/mol, such as thoseaccording to one of the first three embodiments as described above. In afifteenth aspect, the energy gap E_(g) is less than approximately 379kcal/mol, such as those according to one of the first three embodimentsas described above. In a sixteenth aspect, the energy gap E_(g) is lessthan approximately 376 kcal/mol, such as those according to one of thefirst three embodiments as described above. In a seventeenth aspect, theenergy gap E_(g) is less than approximately 373 kcal/mol, such as thoseaccording to one of the first three embodiments as described above. Inan eighteenth aspect, the energy gap E_(g) is less than approximately370 kcal/mol, such as those according to one of the first threeembodiments as described above.

In a nineteenth aspect of the fourth embodiment, the formulation furtherincludes a catalyst. The catalyst is described further in a latersection.

In a fifth embodiment of the present invention, alternative to includingthe oxidizable additive in the formulation, a precursor to theoxidizable additive may be included. The oxidizable additive isaccording to any of the first four embodiments. The precursor may beprimarily in an amorphous state, for example, having a crystallinity ofless than 15%. If the crystallinity is too high, such as higher than15%, it may be too slow or difficult to cause chemical reaction to theprecursor. If a precursor is not received in the primarily amorphousstate, it may be converted into such a state by any suitable method. Forexample, it may be heated to a molten state and rapidly cooled (or“quenched”) to the ambient or low temperature.

Alternatively, it may be dissolved in a solvent, and be “quenched” outof the solution by the addition of a second solvent. In a first aspectof this embodiment, the precursor turns into one of the oxidizableadditives by going through a thermal-induced chemical reaction. For afirst example, the thermal-induced chemical reaction occurs during aregular injection-molding process to form, such as, a plastic container.For a second example, the thermal-induced chemical reaction occursduring a reactive extrusion process. Reactive extrusion conditions maybe selected by any known methods. Graeme Moad provides an exemplary setof conditions in FIG. 1 and the accompanying description of the journalarticle known as Macromol. Symp. 2003, 202, 37, entitled “ControlledSynthesis of Block Polyesters by Reactive Extrusion,” (“Moad”) which isincorporated by reference in its entirety. Gunter Beyer's book entitled“Reactive Extrusion: Principles and Applications” (ISBN: 3527801553), atpage 32, provides another set of conditions for reactive extrusion. Theentirety of the book is incorporated here by reference. The oligoesterof Moad or the ethylene glycol of Beyer may be replaced by a glycol, anamine, polyglycol, polyamine, polyester, polyamide, or combinationsthereof, having an oxygen scavenging moiety. Without being limited bythe theory, the reaction between these alternative molecules tether theoxygen scavenging moiety onto the polyester by way of hydrolysis,condensation, transesterification, transamidation, and/ortransesteramindation reactions, or more generally referred to as“exchange reactions.” Accordingly, any catalysts employed to facilitatesuch reactions are generally referred to as “exchange catalysts.”Conditions may be adjusted based on the property of the compositions andfollowing any known principles and methods, such as those principles andmethods disclosed in Beyer. For a third example, the thermal-inducedchemical reaction occurs independent of and separate from the processingof the formulation. In a first instance for the third example, thethermal-induced chemical reaction occurs in a reactive extrusion processseparated from the injection molding. In a second instance for the thirdexample, it occurs in a normal chemical reaction vessel. In a secondaspect of this embodiment, the precursor interacts with the base resinto form the oxidizable additive as described in any of the earlierembodiments. For example, the base resin is a polyester, the precursoris an amine-based molecule, such as benzylamine, meta-, ortho-, orpara-xylene diamine, and the precursor reacts with the polyester to forman amide-based oxidizable additive. For another example, the base resinis a polyester, and the precursor is an alcohol-based molecule, such aspolybutylene glycol oligomer, polymer fragment or co-polymer fragment,which reacts with the polyester to form ester-based oxidizable additive.In both examples, an effective amount of catalyst may or may not beincluded in the formulation to facilitate the reaction with the baseresin. The catalyst may be any proper exchange catalyst forcondensation, hydrolysis, transesterification, transamidation, and/ortransesteramidation reactions, such as transition metal oxides,hydroxides or alkoxides. For a first instance, the exchange catalyst maybe an oxide, hydroxide or alkoxide of titanium, tin, zirconium or thelike. Other exchange catalysts may not be as effective. In a thirdaspect of this embodiment, the precursor turns into the oxidizableadditive following external stimulation such as ultraviolet radiation,electron beam radiation, plasma radiation, visible light radiation, etc.In a fourth aspect of this embodiment, the precursor turns into theoxidizable additive following the interaction of the precursor withoxygen. In a fifth aspect of this embodiment, the precursor turns intothe oxidizable additive following the interaction with a molecule insideor outside the container, wherein the precursor is embedded inside thewall of the container. For example, the molecule is a water molecule.For another example, the molecule is carbon dioxide. For yet anotherexample, the molecule is an aldehyde molecule produced due todegradation of the base resin or other additives.

Catalyst

Typically, the formulation described above further includes anoxidization catalyst, such as a radical-based catalysts. When theoxidizable additive includes a C—H bond with a BDE that is sufficientlylow, however, the oxidization catalyst is optional. The thresholddepends on the application. For example, the catalyst may be optionalwhen the C—H bond dissociation energy is lower than 65 kcal/mol. Foranother example, the catalyst may be optional when the C—H bonddissociation energy is lower than 70 kcal/mol. For yet another example,the catalyst may be optional when the C—H bond dissociation energy islower than 75 kcal/mol. Without being bound by theory, if the C—H bonddissociation energy is higher than the threshold, there may not besufficient thermal energy to initiate the radical reaction, therefore,the catalyst is needed to generate that initial radical.

The oxidization catalyst may be any catalyst that facilitates theoxidation of an activated C—H bond. Such catalysts may be anyfunctionable transition metal catalyst known in the art, for example,cobalt, manganese, and iron. Alternatively, a precursor to the oxidationcatalyst may be used. The amount of these catalysts or catalystprecursors (hereinafter collectively “catalysts”) to be included in theformulation are dependent upon the identity, the amount of the scavengerused, as well as the any additional components that exist in theformulation. For example, to determine the right amount of catalystC_(A) for a particular scavenger A at a particular concentration c, aladder of catalyst concentration is tested in conjunction with A at thereactive condition. This ladder of catalyst concentration may includethe catalyst at a concentration of 100 ppb, 200 ppb, 300 ppb, 400 ppb,500 ppb, 750 ppb, 1 ppm, 2ppm, 4 ppm, 8 ppm, 16 ppm, 32 ppm, 64 ppm, 100ppm, 200 ppm, 400 ppm, 800 ppm, etc., as measured by the elemental metalpresent in the catalyst. The number of the data points, the intervals,and specific concentrations may be selected and adjusted based onexperience or specific design of experiment criteria. When certainreactivity is observed at a certain concentration, a second catalystconcentration ladder is designed zooming in around that concentration.For example, if certain reactivity is observed at both 32 ppm and 64 ppmcatalyst level, a second catalyst ladder including catalystconcentrations at 24 ppm, 32 ppm, 40 ppm, 48 ppm, 56 ppm, 64 ppm, 72 ppmmay be conducted to find the catalyst level corresponding to the highestreactivity. This may be repeated until an optimal concentration isreached. The preparation of these reactions typically involves mixingthe scavenger and the right amount of catalyst with or without acarrier. The formulation then goes through the proper processing, suchas injection molding, reactive injection molding, extrusion molding,co-extrusion molding processing. Lamination with adhesive tie layers mayalso be used in certain applications. The samples prepared this way maybe tested using any known oxygen permeability or oxygen scavengingcharacterization methods, such as OxySense, MoCon, or any similar ordissimilar methods. Such processing of the samples are routine in theindustry, and the subsequent characterizations may be performed inparallel. These efforts of finding the optimal level shall not beconsidered undue whether or not the number of experiments is high.Additionally, organocatalysts may be used as the oxidization catalyst.For example, this may include N-hydroxyphthalimide and its radical,phthalimido-N-oxyl and the like. Also, they may be used in conjunctionwith the transition metal catalysts, such as Co, Fe, Mn as aco-catalyst.

For formulations that do use a catalyst, it is mandatory that theformulation is free of catalyst deactivation species and free of labilebonds that is prone to cleavage leading to the formation of catalystdeactivation species during processing or application. For transitionmetal-based catalysts, these species include, for example, halogenradicals, strong ligand field ligands, etc. Without being bound bytheory, these species interact with and deactivates the transition metalcatalyst, thereby killing the reactivities of the formulation. Forexample, if a cobalt carboxylate is used as a catalyst, the formulationshould be free of, e.g. as alkyl chlorides, that generates species(chlorine radicals) capable of interacting with cobalt to form astabilized form of cobalt. It is rationalized that these stabilizedforms of cobalt are not active to interact with molecular oxygen, thusfails as a radical catalyst between oxygen and the oxidizable additive.

Once the target concentration of the oxidization catalyst is optimized,the oxidizable additive and the oxidization catalyst may be processedinto the final product with any available methods or technologies knownmethod in the art. For example, melt-blend is one type of processesoften used to produce plastics containers, trays, etc. with, forexample, injection molding, extrusion molding, stretch blow molding,thermoforming processes, etc. The processes may be optimized, by aperson of ordinary skill in the art, to minimize the degradation of theresin and the components to the formulation, while reaching sufficienthomogeneity.

In melt-blend processes, the plastic resins and the various componentsof the formulation is added at the throat of an injection moldingmachine. The injection molding machine may produce a preform that may belater stretched and blow molded into the shape of a container. Or themachine may instead skip the preform-producing step and form thecontainer in a one-step molding machine. The machine may also produce afilm that may be oriented into a film, and a sheet that may bethermoformed into a tray. Containers of different shapes, sizes,mechanical strengths, etc. may be produced. Both single layer andmulti-layer construction of these containers may also be achieved. Themachine has various parameters that may be tuned to optimize theprocessing condition for these different applications. In addition totuning the parameters to produce a conventionally “good” container forpackaging purposes, these parameters may further be tuned to enhance theactive barrier efficacies of the formulation.

Typically, the melting point and the degradation temperature for allcomponents may be measured in advance by, for example, a differentialscanning calorimetry or a thermogravimetric analysis instrument prior tothe processing. These temperature parameters may be used to determinethe processing conditions. For example, it is generally desirable tomaintain the processing temperature of the formulation at the lowest atwhich all components are in their molten state, taking intoconsideration the shear energy that is present in the process.

The components of the formulation may be dosed into the throat of aninjection molding machine together or separately along with a base resinand other necessary additives, such as a colorant or slip agent. Theymay also be processed with a resin either together or separately fromeach other to form masterbatches of a high concentration, wherein themasterbatch is subsequently further processed with additional componentsand base resins to form the final product. Various physical and chemicalinteractions and reactions may be occurring during the variousprocessing steps.

Therefore, embodiments of the present disclosure provide oxygenscavenging or absorbing compositions that may be applied to variousapplications, such as food, beverage, pharmaceutical packaging, consumercommodity packaging, chemical packaging, etc. In one general aspect, thecomposition includes a polymer at a first weight percentage, afunctional component at a second weight percentage, and an oxidationcatalyst at a third weight percentage. The functional component isselected from an oxidizable additive and a precursor to the oxidizableadditive. The precursor is capable of being converted into theoxidizable additive during processing of the composition at an elevatedtemperature, such as a melt-processing temperature. The third weightpercentage is sufficient to cause the oxidation catalyst to catalyze anoxidation reaction of the oxidizable additive by molecular oxygen duringthe application of the composition. The second weight percentage isgreater than the third weight percentage, and the first weightpercentage is greater than a sum of the second and the third weightpercentages. The oxidizable additive includes an organic moietyincluding a first carbon atom (C) attached to a hydrogen atom (H), afirst group, a second group, and a third group. The first group includesa conjugated unit selected from a double bond, a triple bond, anaromatic ring. The first group further includes a first anchor atom. Thefirst anchor atom has an sp² hybridization, an sp hybridization, or alone pair of valence electrons. The first group is attached to the firstcarbon atom at the first anchor atom. The second group includes aheteroatom and is selected from a triple bond, a C═N unit, a N═O unit, afirst C═O unit attached to the first carbon atom and a second carbonatom, a second C═O unit attached to the first carbon atom and an oxygen,a third C═O unit attached to the first carbon atom and a first nitrogenatom (said first nitrogen atom being attached to a third carbon atom), afirst fragment attached to the first carbon atom at an oxygen, a secondfragment attached to the first carbon atom at a nitrogen, and a thirdfragment having at least three heteroatoms within a spatial distance of4 Å from the first carbon atom (the three heteroatoms includes anitrogen)—provided that the second group is the third fragment if andonly if the first group is an ester attached to the first carbon atomwith an ester oxygen or an amide attached to the first carbon atom withan amide nitrogen. The third group is selected from a hydrogen, an alkylgroup, an aromatic group, a double bond, a triple bond, and aheteroatom—provided that: when the first group is a benzene or a vinyl,the third group does not form a ring containing the first carbon atomand the first anchor atom; when the first carbon atom is attached to acarbonyl group and an oxygen atom, (1) the oxygen atom is attached toone of hydrogen and a double bond, (2) the first carbon atom is furtherattached to one of a hydrogen, a double bond, and an oxygen, or (3) thecarbonyl group is attached to a double bond; when the first carbon atomis attached to a vinyl and to a chalcogen selected from an oxygen, asulfur, and a selenium, (1) the chalcogen is attached to one of aheteroatom, a C═C double bond, a triple bond, and a linear alkyl withmore than four carbon atoms, (2) the vinyl is attached to one of aheteroatom and a double bond having a heteroatom, or (3) the firstcarbon is attached to one of a heteroatom and a double bond having aheteroatom; when the first carbon atom is attached to a benzene and anoxygen, the oxygen is attached to a hydrogen, a vinyl, or a carbonylattached to a vinyl; when the first carbon atom is attached to a benzeneor a vinyl and to a nitrogen atom, the nitrogen atom is attached to acarbonyl of an acetylbenzoate (—C(═O)-p-C₆H₄—C(═O)—O—) moiety, a linearalkyl having more than 4 carbons, an aromatic group, or an allyl. Thecomposition does not include inhibiting species at an amount sufficientto deactivate the oxidization catalyst.

In an embodiment the composition is food and/or beverage contactacceptable. In an embodiment, the composition is pharmaceuticallyacceptable. In an embodiment, the first anchor atom is a first sp²carbon. The first sp² carbon is part of a vinyl or a benzene. The secondgroup attaches to the first carbon atom at a second sp² carbon. Thesecond sp² carbon is a carbonyl carbon of a carbonic acid, an ester, oran amide. In an embodiment, the first carbon atom is attached to abenzene ring, and (1) a carboxylic acid (—COOH) group and a hydroxy(—OH), (2) a first ester group attached to the first carbon with anoxygen and a second ester group attached to the first carbon with acarbon atom, (3) a first amide group attached to the first carbon with anitrogen and a second amide group attached to the first carbon atom witha carbon atom, or (4) a amine group and an a third amide attached to thefirst carbon atom with a carbon atom. In an embodiment, the first carbonatom is attached to a benzene or a vinyl, and where the first carbonatom is further attached to a carbonyl. In an embodiment, the firstgroup is a vinyl or a benzene and is attached to a fourth group at thefirst anchor atom. The fourth group includes a carbonyl unit. In anembodiment, the second group is the C═N unit, and the N of the C═N unitattached to the first carbon atom. In an embodiment, the second group isa N═O unit. The N of the N═O unit is attached to a fourth carbon atom.In an embodiment, the first carbon atom is attached to a benzene or avinyl and to a nitrogen atom. The nitrogen atom is attached to acarbonyl of an acetylbenzoate (—C(═O)-p-C₆H₄—C(═O)—O—) moiety. In anembodiment, the first group is a vinyl or a benzene, and the secondgroup is an acrylate ester oxygen. In an embodiment, the functionalcomponent includes the precursor. The precursor includes a functionalgroup or functional groups selected from allyl alcohol, allylamine,benzyl alcohol, benzylamine, and combinations thereof. In an embodiment,the polymer is a polyester, and the functional component includesbenzylic amide. The composition further includes a metal-based exchangecatalyst. In an embodiment, the first carbon atom and the hydrogen atomform a C—H bond having a homolytic bond dissociation energy of less thanabout 87.5 kcal/mol. In an embodiment, the oxidizable additive includesan ester or amide of a polyamine or polyetheramine. The first carbonatom is the alpha-carbon to the ester or amide (that is, the firstcarbon atom attached to the carbonyl), and the first carbon atom iswithin a spatial distance of 4 Å from at least three heteroatoms. In anembodiment, the polymer is a polyester. The functional component is theprecursor and includes a polyalkylene glycol, a polyamine, apolyetheramine, a polyester, a polyamide, copolymers thereof, orcombinations thereof. The composition further includes a metal-basedexchange catalyst at a catalytically-effective amount to catalyze anexchange reaction between the polyester and the precursor.

In one general aspect, the composition also includes a thermoplasticpolymer, a functional component selected from an oxidizable additive anda precursor to the oxidizable additive, and a catalytically-effectiveamount of oxidation catalyst for catalyzing an oxidation reaction of theoxidizable additive by molecular oxygen at a refrigerated, ambient, ornear-ambient temperature. The precursor is capable of being convertedinto the oxidizable additive during processing of the composition at amelt-processing temperature. The oxidizable additive has a formulaselected form (I)-(III) below:

At least one of R₁ and R₂ includes a fragment selected from the groupconsisted of formulae (A)-(D):

Ar₁ may be any organic or organometallic aromatic substituent; R₃ may beselected from hydrogen (H), an organic residue, and an organometallicresidue; X, Y, X₁, and Y₁ may each be independently selected from thegroup consisted of CR₀, SiR₀, N, P; Z, Q, Z₁, are each independentlyselected from the group consisted of O, S, NR₀, PR₀. R₀ is selected fromH, or any organic or organometallic residue. For the structure of (I),when R₁ is (A), R₃ does not form a ring with C₂. For the structure of(II), when R₁ is (A) or (C), X is different than Y. For the structure(III), (1) R₁ and R₂ are both selected from (A)-(D) and different fromeach, (2) R₁ is selected from (B)-(D) and R₂ is selected from aconjugated group, or (3) R₁ is selected (D) and R₂ includes at leastthree heteroatoms within a spatial distance of 4 Å from the first carbonatom. The three heteroatoms including a nitrogen. The composition doesnot comprise inhibiting species at an amount sufficient to deactivatethe oxidization catalyst.

In one general aspect, the composition also includes a plastic material,a radical-based catalyst, and an oxygen scavenger. The oxygen scavengerhas a first carbon atom attached to a hydrogen forming a C—H bond. TheC—H bond has a homolytic bond dissociation energy of less than about87.5 kcal/mol. The first carbon atom further attached to (1) a strongmesomeric electron-donating group and a strong mesomericelectron-withdrawing group, or (2) a conjugated group and a mesomericgroup. The conjugated group is selected from an aromatic group, a doublebond, and a triple bond. The mesomeric group is selected from anelectron-donating and a mesomeric electron-withdrawing group. Thecomposition also includes where the composition is free of inhibitingspecies for the radical-based catalyst.

Embodiments of the present disclosure also provide a method of applyingthe oxygen scavenging or absorbing compositions to various applications.The method includes receiving a first polymer; receiving a precursor toan oxidizable additive; and receiving an oxidation catalyst. The methodalso includes processing to form a polymer article. The polymer articleincludes the first polymer at a first weight percentage, the oxidizableadditive at a second weight percentage, and the oxidation catalyst at athird weight percentage. The third weight percentage is sufficient tocatalyze an oxidation reaction of the oxidizable additive by molecularoxygen at a refrigerated, ambient, or near-ambient temperature. Thesecond weight percentage is greater than the third weight percentage,and the first weight percentage is greater than a sum of the second andthe third weight percentages. The oxidizable additive includes anorganic moiety including a first carbon atom (C) attached to a hydrogenatom (H), a first group, a second group, and a third group. Theoxidizable additive is described above with respect to the first generalaspect. The processing does not produce inhibiting species at an amountsufficient to deactivate the oxidization catalyst.

In an embodiment, the first polymer is a first condensation polymer. Theprecursor is a recycled article of a second condensation polymer. Theprocessing includes processing the oxidizable additive along with thefirst polymer and the oxidization catalyst at an elevated temperature.The method further includes, before the processing, causing a reactionof a molten form or an amorphous form of the precursor thereby formingthe oxidizable additive. In an embodiment, the first polymer ispolyethylene terephthalate. The precursor is a polymeric benzylic amide.The processing includes processing with a metal-based exchange catalystusing reactive extrusion to form the oxidizable additive. In anembodiment, the first polymer is a polyester, where the precursorincludes an amine group. The processing includes processing withreactive extrusion having a screw design that facilitates increasedshear in an early melt-processing zone relative a shear in a latemelt-processing zone.

Many examples for the various embodiments described above arecommercially available. It should be noted that some of such commercialproducts include stabilizers which may inhibit their oxygen scavengingactivities. Additionally, the polymer resin used as base resin mayinclude inhibiting species which may lead to false negative activity.The synthesis of other molecules above may be achieved via any knownmethods in the chemistry and materials sciences. It is to be understoodthat while purity is important to the extent that impurities cannotinterfere with the oxidization reactions, i.e. the formulation shall befree of inhibiting species (or stabilizer), mixtures of active moleculesor mixtures of an active molecule with inert molecules may notnecessarily be non-functional. For example, if a meta-isomer is anactive oxidizable additive, and it is known that the para- andortho-isomers do not inhibit the reactivity, it is acceptable to use amixture of meta-, para-, and ortho-isomer as the oxidizable additive.Using such a mixture may be advantageous, for example, if the isomersare typically produced in the same reaction as no separation isrequired. Same applies to many other co-product situations. This aspectalleviates some of the synthetic and/or separation difficulties commonto many organic and organometallic reactions.

Many examples for the various embodiments above are commerciallyavailable. More examples are provided below for illustrative purposes.They are intended to only be exemplary and shall not be construed to belimiting in any way or form. These representative examples areapplicable to other members of the described genus. A person of ordinaryskill in the art will be able to make and use embodiments of theinvention without undue experimentation.

Example 1: Producing polyethylene terephthalate (PET) plastic containerwith 3% oxidizable additive and 30 ppm of oxidizable catalyst using a30-ton BOY 22S injection molding machine.

An appropriate amount of compatible crystallized base PET resin pelletsare dried at approximately 120° C. for approximately 15 hours and againat approximately 175° C. for approximately 2 hours immediately prior touse. The purpose of the step is to remove moisture that may be presentin the resin pellets. It is generally desired to reduce the moisturelevel to below 50 parts per million (ppm). A moisture analyzer may beused to verify the level of moisture. Without being bound by theory, itis generally understood that condensation polymers such as PET maydegrade at processing condition in presence of large amount of moisture.Other components of the formulation may be dried as appropriate. Forexample, oxidization catalysts such as cobalt stearate salt is oftenused in the form of PET masterbatches. These masterbatches may be driedsimilar to the PET base resins. The oxidizable additives, if present ina form with substantial amount of moisture, may also be dried,preferably under vacuum at a minimal temperature to remove the moisture.However, it is to be understood that a low moisture level in theoxidizable additive or oxidation catalyst may not be necessary or evenpreferred in all circumstances.

The dried resin pellets are then dosed into the hopper of the injectionmolding machine. The oxidizable additive and oxidization catalyst arefed into separate feeding ports of the injection molding machine. Thebarrel is maintained at a temperature of approximately 264° C.; thesprue heater is set at a temperature of approximately 215° C.; thenozzle heater is set at approximately 35% of the power used to heat thebarrel; the injection pressure is set at approximately 600 psi (20 sec.of hold pressure; 15 sec. cooling time); and the mold is cooled withprocess water at a flow rate of approximately 0.5 LPM.

Example 2: Representative example for measuring the activity towards O₂with OxySense.

Plastic containers produced, for example, according to example 1, is cutinto small pieces and placed in a sealed glass vial, wherein the vialhas a photoluminescent indicator, such as a ruthenium-based dye attachedto its glass wall. The ruthenium dye emits light of an intensityaccording to the concentration of oxygen inside the vial. The lightintensity is then monitored at preset time intervals, for example, at 12hours, 1 day, 3 days, 7 days, 14 days, 30 days, 45 days, and longer ifnecessary, to generate a curve of oxygen content inside the vial as afunction of time. The curvature of the curve is then compared to knownfunctional and non-functional formulations (for example, without theoxidizable additive) to decide the activity of the tested formulation.The storage and monitoring of the samples may be at the operatingtemperature of the formulation, for example, the room temperature, oralternatively, at a slightly higher temperature, such as 40° C., inorder to accelerate the test while not significantly distorting theresults.

Examples 3: Synthesis of N-Benzyl-2-phenylacetamide and derivativesthereof. N-Benzyl-2-phenylacetamide is commercially available. Thefollowing synthetic procedure is provided such that a person of ordinaryskill in the art may modify to optimize the preparation or to derivatizethe molecule.

2.0 mmol of methylphenylacetic acid is first dissolved in 20 mL oftoluene, to which a 10 mol % of nickel dichloride (NiCl₂) is added. Themixture is stirred at 80° C. for 10 min, and 2.4 mmol of benzylamine isadded into the vessel. The vessel is then sealed. The mixture ismaintained at 110° C. for 20 h while maintaining magnetic stirring. Atthe end of the reaction, the vessel is cooled. The reaction mixture isdischarged and filtered. The filtrate is washed with dilute HCl (1mol/L) followed by saturated NaHCO₃ aqueous solution, and subsequentlydried to obtain the product. The solid collected is washed with ethylacetate to recover the catalyst.

This procedure may be modified and optimized. For example,methylphenylacetate may be used in place of methylphenylacetic acid withslight modification of the procedure. For another example, derivatizedmethylphenylacetic acids or esters may be used to produce derivatizedproduct, such as those with nitro-, alkyl, acyl, halogen, alkoxysubstitutions on the phenyl ring. For yet another example, a differentacid or ester may be used as a starting material, such as linear fattyacids. For a further example, derivatized benzylamine may be used, suchas those with fluoro substituent on the benzene ring, and xylenediamines.

Examples 4: Synthesis of N-benzylxanthone imine and derivatives thereof.

Xanthone (9.8 g, 50 mmol) and benzylamine (24.6 mL, 225 mmol) aredissolved in toluene (150 mL) and mixed at 0° C. To the mixture, asolution of titanium (IV) chloride (4.1 mL, 37.5 mmol) in toluene (50mL) is then slowly added. The mixture is stirred at ambient temperaturefor 30 min, and then heated to reflux and maintained for 6 h. After themixture is cooled down to room temperature, diethyl ether (200 mL) isadded to precipitate the products. The reaction mixture is then filteredthrough a pad of Celite. The precipitate is washed with diethyl ether(40 mL) three times. The solvent is then removed under reduced pressure.The resulting product is recrystallized from hexane/toluene to produceN-Benzylxanthone imine as a white solid. Other imines (e.g.N-benzylbenzophenone imine) may be prepared with a similar method.Additional derivatization (e.g. alkylation of the benzylic C—H) may beachieved by known chemical method.

Example 5: A formulation that includes a precursor to an oxidizableadditive. This example illustrates that an oxidizable additive may beproduced during the processing of the formulation.

The injection molding machine is modified with a screw design that hasincreased shears in an early melt-processing zone, and normal shear in alate melt-processing zone. Meta-xylene diamine (MXDA) is uniformlydispersed in a processing aid, preferably a wax-based processing aid, ata weight percentage of, for example, 30%. Titanium isoproxide isuniformly dispersed in the same processing aid at a weight percentageof, for example, 6%. During the operation, PET resin pellets are fedinto the hopper of the injection molding machine. At the same time, thetitanium isoproxide dispersion and the MXDA dispersion are eachseparately fed into the throat of the injection molding machine withperistaltic pumps at appropriate dosing speeds to achieve a targetlet-down ratio (LDR) of 2% MXDA and 30 ppm Ti. Normal processingconditions are modified such that the screw speed is substantiallyreduced to allow the precursor to be completely or mostly converted intothe oxidizable additive. Vacuum devolatization is provided at one of theports to remove volatiles. At a late feeding port of the melt-processingzone, cobalt stearate masterbatch is introduced to achieve a target LDRof 30 ppm Co. These parameters may be modified and optimized to achievemaximal uniformity, and further optimized using concentration ladders asdescribed above to achieve the optimized performance. For example, aperson of ordinary skill in the art may target to facilitatecross-condensation reaction in the early melt-processing zone based onreactive extrusion guidelines, while guarding against excessivedegradations of the components. Additionally and critically, safetyprecautions shall be taken as flammable volatiles may be produced duringthe process.

Example 6: A formulation that includes a precursor to an oxidizableadditive. This example illustrates that an oxidizable additive may beproduced during the processing of the formulation.

The injection molding machine is modified with a screw design that hasincreased shears in an early melt-processing zone, and normal shear in alate melt-processing zone. Titanium isoproxide is uniformly dispersed inthe same processing aid at a weight percentage of, for example, 6%.During the operation, PET resin pellets are fed into the hopper of theinjection molding machine. At the same time, the following componentsare also introduced: (1) the titanium isoproxide dispersion is fed intothe throat of the injection molding machine with a peristaltic pump atan appropriate dosing speed to achieve a target let-down ratio (LDR) of30 ppm Ti; (2) polybutylene glycol is fed into the throat of theinjection molding machine with another peristaltic pump at anappropriate dosing speed to achieve a target LDR of 2%. At a latefeeding port of the melt-processing zone, cobalt stearate masterbatch isintroduced to achieve a target LDR of 30 ppm Co. Normal processingconditions are modified such that the screw speed is substantiallyreduced to allow the precursor to be completely or mostly converted intothe oxidizable additive. Vacuum devolatization is provided at one of theports to remove volatiles. These parameters shall be modified andoptimized to achieve maximal uniformity, and further optimized usingconcentration ladders as described above to achieve the optimizedperformance. For example, a person of ordinary skill in the art shalltarget to facilitate cross-condensation reaction in the earlymelt-processing zone based on reactive extrusion guidelines, whileguarding against excessive degradations of the components. Additionallyand critically, safety precautions shall be taken as flammable volatilesmay be produced during the process.

Example 7: Synthesis of N,N′-Dibenzyl terephthalamide and functionalmixtures thereof.

N,N′-Dibenzyl terephthalamide is commercially available. Below is amethod of producing this molecule (or a functional mixture comprisingthis molecule) from waste or recycled polyesters.

Waste materials, such as those from the municipal recycling facilitiesare first separated into components. The polyester portion, or ideally,the polyalkylene terephthalate portion, of the resulting waste materialis collected, cleaned, dried, and shredded into small pieces with agrinder, pulverizer or the like. Alternatively but preferably, thecollected polyester materials go through an extrusion process in whichthe extrudate is rapidly quenched and cut into small pieces. These smallpieces are then added into a flask with excess amount of benzylamine,and optionally with a catalytically active amount of titanium oxide. Themixture is stirred and maintained at a refluxing temperature overnight.White power is produced, collected, washed with ethanol, dried undervacuum and stored over desiccants. It may be used as an oxidizableadditive according to one or more embodiments of the present disclosure.

The advantage of this method is partly in that there is no need toseparate different types of polyesters, such as between polyethyleneterephthalate and polybutylene terephthalate. Both are converted to thesame product. Additionally, the reaction is relatively insensitive tothe presence of contaminants. For example, polyolefins typically floatat the top of the reaction mixture and may be easily separated outwithout contaminating the final products; and soluble contaminants maybe washed away with benzylamine or alcohol washing solutions, both ofwhich may be distilled and recovered. Moreover, other polyesters fromthe collected waste may produce different, but similarly functionalproducts during the same reaction.

Example 8: Synthesis of N,N′-Dibenzyl terephthalamide and functionalmixtures thereof.

This example provides another method of producing this molecule (or afunctional mixture comprising this molecule) from waste or recycledpolyesters with reactive extrusion. The extruder is first modified tofacilitate cross-condensation reactions, including but not limited to,adopting a screw design that enhances shear during the melt-processing.Titanium ethylhexanoate is uniformly dispersed in a parafin wax-basedprocessing aid at a weight percentage of 6%. Polyester materialseparated from collected waste materials (as described in Example 7) isfed into the hopper of an extruder. Para-xylene diamine (PXDA) and theprepared titanium ethylhexanoate dispersion are each separately fed intothe throat of the extrusion machine with a peristaltic pump atappropriate dosing speeds to achieve a target let-down ratio (LDR) of 5%PXDA and 60 ppm Ti. Normal processing conditions are modified such thatthe screw speed is substantially reduced to allow the polyesters toreact with PXDA. Vacuum devolatization is provided at multiple ports toremove volatiles. The extrudate is immediately quenched and pelletized.The product may be used as a polyester masterbatch of N,N′-Dibenzylterephthalamide capable of being stored and used as an oxidizableadditive as necessary. The above parameters shall be modified andoptimized to achieve maximal uniformity, and further optimized usingconcentration ladders as described above to achieve the optimizedperformance. For example, a person of ordinary skill in the art shalltarget to facilitate cross-condensation reaction based on reactiveextrusion guidelines, while guarding against excessive degradations ofthe components. Additionally and critically, safety precautions shall betaken as flammable volatiles may be produced during the process.

Example 9: Polyamide as oxidizable additive with reduced haze.Meta-xylene diamine (MXDA) is used as the oxidizable additive at a levelof 7% along with cobalt stearate as the oxidization catalyst at a levelof 50 ppm. The operating condition is according to Example 1 describedabove with the exception that (1) a Husky injection molding machine isfirst used in place of the BOY to produce a preform, which issubsequently converted into a bottle using a Sidel blow-molding machine;(2) the MXD6 pellets, after dried and before being dosed into injectionmolding machine, is first coated with a thin film of titanium2-ethylhexanoate by immersion in the solution. The resultant containerhas reduced haze as compared to formulations in which the MXD6 is notfirst treated with titanium alkoxide. Alternatively, the titanium2-ethylhexanoate may instead be separately fed into the throat of theHusky with a peristaltic pump at an optimized speed to achieve theminimized haze.

Example 10: Oligomers and polymers as oxidizable additive. Itaconic acid(IA) is combined with various polyols (trimethylolpropane; sorbitol;1,4-cyclohexanedimethanol; poly(ethylene glycol);3-methyl-1,5-pentainediol) with or without the presence of additionaldiacids (adipic acid or succinic acid). The mixture is then heated to120-150° C. with thermal or enzymatic polymerization to form oligomersor polymers. This forms copolymers with oxidizable itaconic moiety as acomonomer, therefore is an oxidizable additive.

Example 11:2-bromo-1-(3-ethyl-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)ethan-1-oneis commercially available.

Example 12: 1,2,3,4,5,6,7,8,9,10,11,12-dodecahydrotriphenylene iscommercially available. It may be used as an oxidizable additive.

Example 13: Synthesis of Benzylidenebenzylamine and derivatives thereof.Benzylidenebenzylamine is commercially available and may also besynthesized as follows. The following synthetic procedure is providedsuch that a person of ordinary skill in the art may modify to optimizethe preparation or to derivatize the molecule, such as by includingsubstituents on the benzene rings of the starting materials. 20 mmol ofbenzene aldehyde is slowly added to a well-cooled stirred solution ofbenzylamine (1 eq.) over 30 min at 0° C. The reaction mixture is thenallowed to stand till the two layers separated completely. The organiclayer is separated and stored over KOH pellets. Precautions shall betaken in handling this product to avoid moisture.

Example 14: Synthesis of Benzylidenebenzylamine oligomer or polymer.Oligomer or polymers counterpart of Benzylidenebenzylamine may beproduced using the same method as in Example 13 with the exception thata diamine, such as MXDA, and benzene dialdehyde are used instead.Oligomers and polymers may be preferable due to the reduced migrability.Furthermore, the extended conjugation may provide color-indication.

Example 15: Synthesis of nitrosomethylbenzene and derivatives thereof 1mmole of N-benzylhydroxylamine is dissolved in 10 ml of previously driedmethylene chloride and is cooled at 0° C. 0.85 g of silver carbonatereagent is added into the solution under vigorous stirring. Blackprecipitates formed over stirring for 10 min at 0° C. The blackprecipitate is filtered off through a pad of Celite in a frit, and alsowashed well with ice-cold methylene chloride. The solvent is thenevaporated at 0° C. using a rotary evaporator. Cold pentane is used towash off the benzaldoxime to obtain pure trans-dimericnitrosomethylbenzene. This material is stored in its crystalline form asa dimer. The product is relatively unstable and is preferred to bestored in crystalline form. It may be dissolved or suspended in aprocessing carrier, such as polyethylene glycol, at a low temperatureimmediately before processing, and dosed into the injection moldingmachine with a peristaltic pump.

Example 16: Synthesis of N-benzyl-4-methoxy-N-methyl-benzenesulfonamideand derivatives thereof. 74 mg of [MeCN]₄Cu(I)PF₆ (0.2 mmol, 10 mol %),44 mg of 1,3-indanedione (0.3 mmol, 15mol %), and 402 mg of N-methyl4-methoxybenzenesulfonamide (2.0 mmol, 1.0 eq.) are weighed into a 20 mLvial equipped with a magnetic stir bar. Toluene (5.3 mL, 50 mmol, 25equiv) is added to dilute the mixture and stirring is maintained at roomtemperature for 15 min. At the end of the reaction, 1.05 g of3—CF₃C₆H₄CO₃-t-Bu oxidant (4.0 mmol, 2.0 equiv) is added via sryinge ina single batch. The vial is fitted with a septum or Teflon-coated capand purged with nitrogen. The mixture is then stirred at roomtemperature for 3 days. The resulting mixture is poured into a 125 mLseparatory funnel containing 75 mL of aqueous sodium carbonate. Themixture is then extracted with ethyl acetate (30 mL) three times. Thecombined organic layers are washed with 30 mL of brine and dried overMgSO₄. The mixture is then filtered, concentrated under reduced vacuum,and purified by column chromatography through silica gel. A gradient of100% hexanes to 20% ethyl acetate in hexanes is used as the eluant toseparate the target compound as an off-white solid.

Example 17. Exemplary method for reactive extrusion of a polyester andan oxidizable additive having an ester group. Experiments are performedon a JSW TEX 30 twin screw extruder having a 30 mm screw diameter and anoverall LID of 42 [comprising ten temperature controlled barrel sectionsof LID 3.5, three unheated sampling monitoring blocks of L/D 1.167 and acooled feed block of LID 3.5]. The PET and the oxidizable additive arefed into the extruder using a JSW TTF20 gravimetric feeder and a K-TronKQX gravimetric feeder respectively. The extruder is operated inco-rotating (intermeshing self wiping) modes with throughputs of between1 and 5 kg/h. The screw design consists of kneading, conveying andreversing elements as shown in Moad's FIG. 1. Screw speed is routinelyset at 155 rpm (40% of motor output). The residence times are 37 minutesfor a throughput rate of 1 kg/h, 17 minutes for 2 kg/h and 5 minutes for5 kg/h. The barrel temperature profile is as shown in Moad's FIG. 1. Themelt temperatures and pressures are monitored at three points along thebarrel as well as in the die. The extrudate is air-cooled by passagealong a conveyor belt and pelletized. The oxidizable additive are meltblended at levels of 5-20 mole % of repeat units with PET. The pelletsare injection molded with 80 ppm of cobalt catalyst into plasticarticles of chosen shape.

Example 18. The following commercially available molecules have beenidentified: 1,3-diphenylacetone oxime, Indene,1,3,5-Tribenzylhexahydro-1,3,5-triazine, 4-Allylanisole, Allylbenzene,3-Phenyl-1-propyne, Diphenylacetic acid, Itaconic acid, Dimethylitaconate, 1-Naphthylacetic acid, Homophthalic acid, DL-Mandelic acid,2-hydroxy-2-phenylacetic acid, 2- Methoxyphenylacetic acid,(3,4-Dimethoxyphenyl)acetic acid, 3,4-Dihydroxyphenylacetic acid,Homophthalic anhydride, ethyl 2-(4-nitrophenyl)acetate, ethyl4-methoxyphenylacetate, Ethyl 4-chlorophenyl acetate, Ethyl4-bromophenyl acetate, methyl 4-hydroxyphenylacetate,3-(benzyloxy)-3-oxo-2-phenylpropanoic acid, Methyl4-fluorophenylacetate, methyl 9H-xanthene-9-carboxylate, Ethyl2-methylphenylacetate, Methyl 4-chlorophenylacetate, Methyl3-chlorophenylacetate, Methyl 3-methylphenylacetate, Methyl2,6-dichlorophenylacetate, 2-(acetyloxy)-2-phenylacetic acid,BOC-L-alpha-phenylglycine, 2-(acetylamino}-2-phenylacetic acid,BOC-O-alpha-phenylglycine, N-BOC-4-Fluorophenylglycine,5-phenylimidazolidine-2,4-dione,3-hexyl-5-phenylimidazolidine-2,4-dione,3-methyl-5-phenyl-1,3-oxazolane-2,4-dione, 2-Phenylbutyramide,3-(2-pyridinylmethyl)-1,3-dihydro-2H-indol-2-one, Carbenicillin disodiumsalt, 9H-xanthene-9-carboxamide, dibenzylmaleate, dibenzylfumarate,3-(3-methoxyphenyl)-1-methylazepan-2-one, 3-methyl-5-phenyl-1,3-oxazolane-2,4-dione, benzyl acrylate, 5-bromo-3-hydroxyindolin-2-one,5-fluoro-3-hydroxylndolln-2-one, Tolazoline hydrochloride,N′-hydroxy-2-phenylethanimidamide,2-({[(1-benzyl-2-phenylethylidene)amino]oxy}carbonyl)-3-chloro-1-benzothiophene,2-{[3-({[1-(2-hydroxyphenyl)ethylidene]amino}methyl)benzyl]ethanimidoyl}phenol,2-[(1,3 -benzodioxol-5-ylmethyl)ethani midoyl] phenol,2-(benzylethanimidoyl)phenol, 1-Naphthylacetic acid, Homophthalic acid,2-Methoxyphenylacetic acid, (3,4-Dimethoxyphenyl)acetic acid,3,4-Dihydroxyphenylacetic add, 4-Methoxyphenylacetic acid,4-Nitrophenylacetic acid, Methyl alpha-bromophenylacetate,1,3-isochromandione, Ethyl phenylcyanoacetate, Homophthalic anhydride,4-Hydroxyphenylacetamide, 5-chloroindolin-2-one,5-bromo-1-methyl-2-oxoindoline, 5-amino-1-methyl-2-oxoindoline,Nl-(2-oxopropyl)-2-phenylacetamide, 6-Bromooxindole,5-(bromoacetyl)-2-oxoindoline, Benzyl cinnamate, Benzyl benzoate,4-Vinylbenzyl acetate, gamma-Benzyl L-glutamate, Triallylamine, Benzylchloroacetate, Vinylacetic acid, trans-Styrylacetic acid, Itaconicanhydride, Methyl 3-hexenoate, 2-(4-isobutylphenyl)propanenitrile,2-(4-chlorophenyl)-3-oxopropanenitrile, 2,3-diphenylsuccinonitrlle,2,3-dlphenylpropanenitrlle, Triallyl-s-triazine-2,4,6(1H,3H,5H) -trione,1,3,5-Benzenetricarboxylic acid triallyl ester, tribenzylamine oxide,tribenzylphosphine oxides, Diallylamine, Diallylmethylamine, Diethylallylphosphonate, Allyltriphenylphosphonium bromide, Triethyl4-phosphonocrotonate, Allyltrlphenylphosphonium chloride, Diethylbenzylphosphonate, Benzyltriphenylphosphonium chloride, Malononitrile,Dicyanomethane, 3-oxoindane-1-carboxylic acid.

The above examples are provided merely for illustrative purposes. Aperson of ordinary skill in the art understands that these examples maybe modified in various aspects to optimize the formulation for variousdifferent applications without departing from the spirit of the theinvention. Additionally, these examples shall not be limited to thecontexts in which they are described. Rather, they shall be deemedapplicable to those additional applications with similar reactiveenvironments. Other embodiments of the invention, while not specificallydescribed, will become apparent to those skilled in the art from readingthe disclosure and applying the disclosure to experiments.

INDUSTRIAL APPLICABILITY

Embodiments of this present disclosure may be used in various packagingapplications to extend the shelf life of the contents by (1) reduceinitial headspace oxygen and/or (2) impede oxygen ingress. They may beused in food, beverage, drug applications for human and/or animals. Theymay be used in consumer products and/or chemical packaging. Embodimentsof this present disclosure also provide methods that may used associatedwith the above applications. Embodiments of this present disclosure mayalso be used in the recycling industry, to convert recycled plasticsinto oxygen scavengers provided herein.

1. A composition for an application at a refrigerated, ambient, ornear-ambient temperature, comprising: a polymer at a first weightpercentage; a functional component selected from an oxidizable additiveand a precursor to the oxidizable additive, the functional component ata second weight percentage; and an oxidation catalyst at a third weightpercentage sufficient to catalyze an oxidation reaction of theoxidizable additive by molecular oxygen during the application of thecomposition, wherein the precursor is capable of being converted intothe oxidizable additive during processing of the composition at anelevated temperature, wherein the second weight percentage is greaterthan the third weight percentage, and the first weight percentage isgreater than a sum of the second and the third weight percentages,wherein the oxidizable additive comprises an organic moiety including afirst carbon atom (C), the first carbon atom being directly attached toa hydrogen atom (H), and the first carbon atom further being directlyattached to: (1) each of a first group, a second group, and a thirdgroup, or (2) each of a strong mesomeric electron-donating group and astrong mesomeric electron-withdrawing group, wherein the first groupincludes a conjugated unit selected from a double bond, a triple bond,an aromatic ring, the first group further includes a first anchor atom,the first anchor atom has an sp² hybridization, an sp hybridization, ora lone pair of valence electrons, and the first group is directlyattached to the first carbon atom at the first anchor atom, wherein thesecond group includes a heteroatom and the second group is selected froma triple bond; a C═N unit; a N═O unit; a first C═O unit directlyattached to the first carbon atom and directly attached to a secondcarbon atom; a second C═O unit directly attached to the first carbonatom and directly attached to an oxygen; a third C═O unit directlyattached to the first carbon atom and directly attached to a firstnitrogen atom, said first nitrogen atom being directly attached to athird carbon atom; a first fragment directly attached to the firstcarbon atom at an oxygen; a second fragment directly attached to thefirst carbon atom at a nitrogen; and a third fragment having at leastthree heteroatoms within a spatial distance of 4 Å from the first carbonatom, the three heteroatoms including a nitrogen, provided that thesecond group is the third fragment if and only if the first group is anester directly attached to the first carbon atom with an ester oxygen oran amide directly attached to the first carbon atom with an amidenitrogen, wherein the third group is selected from a hydrogen, an alkylgroup, an aromatic group, a double bond, a triple bond, and aheteroatom, provided that: when the first group is a benzene or a vinyl,the third group does not form a ring containing the first carbon atomand the first anchor atom, when the first carbon atom is directlyattached to a carbonyl group and directly attached to an oxygen atom,(1) the oxygen atom is directly attached to one of hydrogen and a doublebond, (2) the first carbon atom is further directly attached to one of ahydrogen, a double bond, and an oxygen, or (3) the carbonyl group isdirectly attached to a double bond, when the first carbon atom isdirectly attached to a vinyl and to a chalcogen selected from an oxygen,a sulfur, and a selenium, (1) the chalcogen is directly attached to oneof a hydrogen, heteroatom, a triple bond, and a linear alkyl with morethan four carbon atoms, (2) the vinyl is directly attached to one of aheteroatom and a double bond having a heteroatom, or (3) the firstcarbon is directly attached to one of a heteroatom separated from thechalcogen, and a double bond having a heteroatom separated from thechalcogen, when the first carbon atom is directly attached to a benzeneand directly attached to an oxygen, (1) the oxygen is directly attachedto one of a hydrogen, a vinyl, and a carbonyl directly attached to avinyl, or (2) the first carbon atom is further attached to a carbonylgroup, when the first carbon atom is directly attached to a benzene or avinyl and directly attached to a nitrogen atom, (1) the nitrogen atom isdirectly attached to a carbonyl of an acetylbenzoate(—C(═O)-p-C₆H₄—C(═O)—O—) moiety, directly attached to one of a linearalkyl having more than 4 carbons, an aromatic group, and an allyl, or(2) the first carbon atom is further directly attached to a carbonylgroup, wherein the strong mesomeric electron-donating group is selectedfrom a phenoxide (—O⁻) group, an amine (—NR₂, —NHR, —NH₂) group, anether (—OR) group, and a hydroxy (—OH) group, wherein the strongmesomeric electron-withdrawing group selected from a cyano (CN) group, atriflyl (—SO₂CF₃) group, a sulfonate (—SO₃H) group, a nitro (—NO₂)group, and wherein the composition does not comprise inhibiting speciesat an amount sufficient to deactivate the oxidization catalyst.
 2. Thecomposition of claim 1, wherein the first anchor atom is a first sp²carbon, the first sp² carbon being part of a vinyl or a benzene, andwherein the second group directly attaches to the first carbon atom at asecond sp² carbon, the second sp² carbon being a carbonyl carbon of acarbonic acid, an ester, or an amide.
 3. The composition of claim 1,wherein the first carbon atom is directly attached to a benzene ring,and (1) a carboxylic acid (—COOH) group and a hydroxy (—OH), (2) a firstester group directly attached to the first carbon with an oxygen and asecond ester group directly attached to the first carbon with a carbonatom, (3) a first amide group directly attached to the first carbon witha nitrogen and a second amide group directly attached to the firstcarbon atom with a carbon atom, or (4) an amine group and an a thirdamide directly attached to the first carbon atom with a carbon atom. 4.The composition of claim 1, wherein the first carbon atom is directlyattached to a benzene or a vinyl, and wherein the first carbon atom isfurther directly attached to a carbonyl.
 5. The composition of claim 1,wherein the functional component is selected from mandelic acid,mandelide, polymandelic acid, and polymandelide.
 6. The composition ofclaim 1, wherein the first group is a vinyl and is directly attached toa fourth group at the first anchor atom, the fourth group including acarbonyl unit.
 7. The composition of claim 1, wherein the second groupis the C═N unit, the N of the C═N unit directly attached to the firstcarbon atom.
 8. The composition of claim 1, wherein the second group isa N═O unit.
 9. The composition of claim 8, wherein the N of the N═O unitis attached to a fourth carbon atom.
 10. The composition of claim 1,wherein first carbon atom is directly attached to a benzene or a vinyland to a nitrogen atom, the nitrogen atom is directly attached to acarbonyl of an acetylbenzoate (—C(═O)-p-C₆H₄—C(═O)—O—) moiety.
 11. Thecomposition of claim 1, wherein the first group is a vinyl or a benzene,and the second group is an acrylate ester oxygen.
 12. The composition ofclaim 1, wherein the functional component includes the precursor, andwherein the precursor includes a functional group or functional groupsselected from allyl alcohol, allylamine, benzyl alcohol, benzylamine,and combinations thereof.
 13. The composition of claim 1, wherein thepolymer is a polyester, the functional component includes benzylicamide, the composition further comprising a metal-based exchangecatalyst configured to catalyze an exchange reaction between thepolyester and the functional component.
 14. The composition of claim 1,wherein the first carbon atom and the hydrogen atom form a C—H bondhaving a homolytic bond dissociation energy of less than about 87.5kcal/mol.
 15. The composition of claim 1, wherein the oxidizableadditive includes an ester or amide of a polyamine or polyetheramine,wherein the first carbon atom is part of an alkoxy group of the ester orpart of an amine group of the amide, and the first carbon atom is withina spatial distance of 4 Å from at least three heteroatoms.
 16. Thecomposition of claim 1, wherein the polymer is a polyester, thefunctional component is the precursor and includes a polyalkyleneglycol, a polyamine, a polyetheramine, a polyester, a polyamide,copolymers thereof, or combinations thereof, and the composition furthercomprises a metal-based exchange catalyst at a catalytically-effectiveamount to catalyze an exchange reaction between the polyester and theprecursor.
 17. A composition, comprising: a thermoplastic polymer; afunctional component selected from an oxidizable additive and aprecursor to the oxidizable additive; and a catalytically-effectiveamount of oxidation catalyst for catalyzing an oxidation reaction of theoxidizable additive by molecular oxygen at a refrigerated, ambient, ornear-ambient temperature, wherein the precursor is capable of beingconverted into the oxidizable additive during processing of thecomposition at a melt-processing temperature, wherein the oxidizableadditive has a formula selected form (I)-(IV) below:

wherein at least one of R₁ and R₂ includes a fragment selected from thegroup consisted of formulae (A)-(D):

wherein Ar₁ may be any organic or organometallic aromatic substituent;R₃ may be selected from hydrogen (H), an organic residue, and anorganometallic residue; X, Y, X₁, and Y₁ may each be independentlyselected from the group consisted of CR₀, SiR₀, N, P; Z, Q, Z₁, are eachindependently selected from the group consisted of O, S, NR₀, PR₀, andCR₀R₄, wherein R₀and R₄ are independently selected from H, or anyorganic or organometallic residue; E is selected from O, N, P, N═O, andP═O, wherein for the structure of (I), when R₁ is (A), R₃ does not forma ring with C₂, when R₂ is (A), R₁ is a benzoate (—C₆H₄—C(═O)—O—) moietysuch that the structure (I) includes a —C(═O)—C₆H₄—C(═Z)-Q-fragmentdirectly attached to the R₂, or Q is O; wherein for the structure of(II), when R₁ is (A) or (C), X is different than Y; wherein for thestructure (III), (1) R₁ and R₂ are both selected from (A)-(D) anddifferent from each, (2) R₁ is selected from (B)-(D) and R₂ is selectedfrom a conjugated group, or (3) R₁ is selected (D) and R₂ includes atleast three heteroatoms within a spatial distance of 4 Å from the firstcarbon atom, the plurality of heteroatoms including a nitrogen, whereinfor the structure (IV), (1) E is selected from N and P, and is directlyattached to at least one (C) group, (2) E is selected from N═O and P═O,and is directly attached to at least one of (A), (B), and (C), or (3) Eis O, and is directly attached to (C), provided that E is furtherdirectly attached to one of a hydrogen, a heteroatom, a triple bond, anda linear alkyl with more than four carbon atoms, and wherein thecomposition does not comprise inhibiting species at an amount sufficientto deactivate the oxidization catalyst.
 18. A composition, comprising: aplastic material; a radical-based catalyst; and an oxygen scavengerhaving a first carbon atom attached to a hydrogen forming a C—H bond,the first carbon atom further attached to a first moiety, a secondmoiety and a third moiety, wherein the first carbon atom is furtherdirectly attached to: (1) a first group selected from a phenoxide (—O⁻)group, an amine (—NR₂, —NHR, —NH₂) group, an ether (—OR) group, and ahydroxy (—OH) group; and a second group selected from a cyano (CN)group, a triflyl (—SO₂CF₃) group, a sulfonate (—SO₃H) group, and a nitro(—NO₂) group, (2) a third group selected from B(OH)₃—, (CH₂)₃—, (CH₂)₄—,(CH₂)₅— and derivatives thereof; a fourth group selected from acarboxylate (—COOR₄) group directly attached to the first carbon atomwith a carbonyl carbon of the carboxylate group, and derivativesthereof; and a fifth group selected from a benzene and a C═C double bonddirectly attached to the first carbon atom, or (3) a sixth groupselected from thiolate anion (—S⁻) group, an oxide anion (—O⁻) group, anamine (—NR₂, —NHR, —NH₂) group, an ether (—OR) group, and a hydroxy(—OH) group, amide (—NHCOR) group, an ester (—OCOR) group, a sulfonamide(—NHS(═O)₂R) group, a styryl (—CH═CH—C₆H₅) group, a ferrocenyl group, atriphenylphosphine imide (—N═P(C₆H₅)₃) group, a thiol (—SH) group, aphosphonic dichloride (—P(═O)Cl₂) group, an isocyanate (—N═C═O) group,an alkyl groups, a methylenedioxy (—OCH₂—) group, a vinyl (—CH═CH₂)group, a trialkyltin (—Sn(CH₃)₃) group, a furyl group, a thienyl goup, atetramethylsilane (—CH₂—Si(CH₃)₃) group, and derivatives thereof; aseventh group selected from a cyano (CN) group, a triflyl (—SO₂CF₃)group, a trihalide group (—CF₃, —CCl₃), a sulfonate (—SO₃H) group, anitro (—NO₂) group, a nitrosyl (—NO) group, an aldehyde (—CHO) group, aketone (—COR) group, a carboxylic acid (—COOH or —COO⁻) group, an acylchloride (—COCl) group, an esters (—COOR) group, and an amide (—CONH₂)group, a nitrogen cation (—N⁺≡N) group, an arsenic acid (As(O)(OH)₂ orAsO₃H⁻) group, a sulfonamide (—S(═O)₂NHR, (—S(═O)₂NR₂) group, atrifluoromethyl (—CF₃) group, methylsulfinate (—SO₂(CH₃)) group,methylsulfenate (—SOCH₃) group, thiocyanate (—SCN) group, alkyne (—C≡CH)group, vinyl directly attached to an electron-withdrawing groups R₅(—CH═CH-R₅), a dialkyl phosphoryl (—P(═O)R₂) group, a dialkylthiophosphoryl (—P(═S)R₂) group, a dialkylphosphine (—PR₂) group, atetramethylphosphonium (—P(CH₃)₄ ⁺) group, pyridyl groups, a benzoxazolegroup, a benzothiazolyl group, a conjugated group or hyperpolarizableatom directly bonded to perfluorinated alkyl groups, and derivativesthereof; and an eighth group selected from an aromatic group, an alkenylgroup, and a alkynyl group; and wherein R and R₄ are independently anyorganic or organometallic residue, and R₅ is selected from a cyano (CN)group, a triflyl (—SO₂CF₃) group, a sulfonate (—SO₃H) group, and a nitro(—NO₂) group. 19-22. (canceled)
 23. The composition of claim 1, whereinthe second group is selected from a nitrile group, an isonitrile group,and a C≡C triple bond.
 24. The composition of claim 1, wherein thesecond group is a double bond having a nitrogen.